KR20210147290A - Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same - Google Patents
Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same Download PDFInfo
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- KR20210147290A KR20210147290A KR1020200064285A KR20200064285A KR20210147290A KR 20210147290 A KR20210147290 A KR 20210147290A KR 1020200064285 A KR1020200064285 A KR 1020200064285A KR 20200064285 A KR20200064285 A KR 20200064285A KR 20210147290 A KR20210147290 A KR 20210147290A
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- KR
- South Korea
- Prior art keywords
- formula
- compound represented
- catalyst composition
- substituted
- unsubstituted
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 173
- 239000000203 mixture Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 79
- 230000008569 process Effects 0.000 title description 3
- 230000003197 catalytic effect Effects 0.000 title description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 79
- 150000001336 alkenes Chemical class 0.000 claims abstract description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims description 192
- -1 cationic Lewis base Chemical class 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 41
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 40
- 229910052796 boron Inorganic materials 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 21
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims description 15
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 claims description 15
- 229910052735 hafnium Inorganic materials 0.000 claims description 14
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 10
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 9
- 125000001118 alkylidene group Chemical group 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 6
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910007926 ZrCl Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 claims description 3
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229910052795 boron group element Inorganic materials 0.000 claims description 3
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 claims description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 claims description 3
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 3
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 3
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 3
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 claims description 3
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 3
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 claims description 3
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 claims description 3
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 claims description 3
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 claims description 2
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 claims 1
- QGHZYTQKNCPPTK-UHFFFAOYSA-N cyclopentylalumane Chemical compound C1(CCCC1)[AlH2] QGHZYTQKNCPPTK-UHFFFAOYSA-N 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 description 15
- 239000012968 metallocene catalyst Substances 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 241000349731 Afzelia bipindensis Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- QEKDVHNXEFFHLF-UHFFFAOYSA-N lithium;1,2,3,4,5-pentamethylcyclopentane Chemical compound [Li].C[C]1[C](C)[C](C)[C](C)[C]1C QEKDVHNXEFFHLF-UHFFFAOYSA-N 0.000 description 2
- QSWRLCZANWKCFF-UHFFFAOYSA-N lithium;5-propylcyclopenta-1,3-diene Chemical compound [Li+].CCC[C-]1C=CC=C1 QSWRLCZANWKCFF-UHFFFAOYSA-N 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YRTOBDBOFWQAQJ-UHFFFAOYSA-L [Cl-].[Cl-].CC1=C(C(=C(C1(C)[Zr+2]C1(C=CC=C1)CCC)C)C)C Chemical compound [Cl-].[Cl-].CC1=C(C(=C(C1(C)[Zr+2]C1(C=CC=C1)CCC)C)C)C YRTOBDBOFWQAQJ-UHFFFAOYSA-L 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Abstract
Description
본 발명은 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물, 이를 포함하는 올레핀 중합용 촉매 및 이들을 제조하는 방법에 관한 것이다. 구체적으로, 본 발명은 중심 금속이 서로 다른 비다리형(non-bridged)의 비스사이클로펜타디에닐(biscyclopentadienyl)기를 갖는 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물, 이를 포함하는 올레핀 중합용 촉매 및 해당 혼성 촉매 조성물 및 촉매를 제조하는 방법에 관한 것이다.The present invention relates to a hybrid catalyst composition comprising a heterogeneous transition metal compound, a catalyst for olefin polymerization comprising the same, and a method for preparing the same. Specifically, the present invention relates to a hybrid catalyst composition comprising a heterogeneous transition metal compound having a non-bridged biscyclopentadienyl group having a different central metal, a catalyst for olefin polymerization comprising the same, and It relates to a hybrid catalyst composition and a method for preparing the catalyst.
폴리올레핀계 중합체는 실생활에서 쇼핑백, 비닐하우스, 어망, 담배 포장지, 라면 봉지, 요구르트 병, 배터리 케이스, 자동차 범퍼, 내장재, 신발 밑창, 세탁기 등의 소재로 다양하게 사용된다.Polyolefin-based polymers are widely used in real life as materials for shopping bags, plastic houses, fishing nets, cigarette wrappers, ramen bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, washing machines, and the like.
종래 폴리에틸렌, 폴리프로필렌 및 에틸렌-알파올레핀 공중합체와 같은 폴리올레핀계 중합체와 이들의 공중합체는 티타늄 화합물과 알킬 알루미늄 화합물로 이루어진 지글러-나타(Ziegler-Natta) 촉매와 같은 불균일계 촉매에 의하여 제조되었다.Conventionally, polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-alpha olefin copolymers and copolymers thereof have been prepared using a heterogeneous catalyst such as a Ziegler-Natta catalyst made of a titanium compound and an alkyl aluminum compound.
최근에는 촉매 활성이 매우 높은 균일계 촉매인 메탈로센 촉매를 이용한 폴리올레핀의 제조방법이 연구되고 있다. 메탈로센 촉매는 전이금속 또는 전이금속 할로겐 화합물에 사이클로펜타디에닐(cycolpentadienyl), 인데닐(indenyl), 사이클로헵타디에닐(cycloheptadienyl) 등의 리간드가 배위 결합된 화합물로서 샌드위치 구조를 기본적인 형태로 갖는다. 이때, 리간드의 형태와 중심 금속의 종류에 따라 다양한 분자 구조를 갖는다.Recently, a method for preparing polyolefin using a metallocene catalyst, which is a homogeneous catalyst with very high catalytic activity, has been studied. The metallocene catalyst is a compound in which ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl are coordinated to a transition metal or transition metal halide compound, and has a sandwich structure in a basic form. . In this case, it has various molecular structures according to the type of ligand and the type of the central metal.
불균일계 촉매인 지글러-나타(Ziegler-Natta) 촉매가 활성점인 금속 성분이 불활성인 고체 표면에 분산되어 활성점의 성질이 균일하지 않은데 반해, 메탈로센 촉매는 일정한 구조를 갖는 하나의 화합물이기 때문에 모든 활성점이 동일한 중합 특성을 갖는 단일 활성점 촉매(single-site catalyst)로 알려져 있다.In a heterogeneous Ziegler-Natta catalyst, the metal component as the active site is dispersed on an inactive solid surface and the properties of the active site are not uniform, whereas the metallocene catalyst is a compound with a certain structure. Therefore, it is known as a single-site catalyst with all sites having the same polymerization properties.
일반적으로, 메탈로센 촉매는 그 자체만으로는 중합 촉매로서의 활성이 없기 때문에, 메틸 알루미녹산 등의 조촉매와 함께 사용된다. 조촉매의 작용에 의하여 메탈로센 촉매가 양이온으로 활성화되고, 동시에 조촉매는 메탈로센 촉매에 배위하지 않은 음이온으로서 불포화된 양이온 활성종을 안정화시켜 각종 올레핀 중합에 활성을 갖는 촉매계를 형성한다.In general, since a metallocene catalyst has no activity as a polymerization catalyst by itself, it is used together with a cocatalyst such as methyl aluminoxane. The metallocene catalyst is activated as a cation by the action of the cocatalyst, and at the same time, the cocatalyst is an anion that is not coordinated with the metallocene catalyst and stabilizes the unsaturated cationic active species to form a catalyst system having activity in various olefin polymerizations.
이러한 메탈로센 촉매는 공중합이 용이하고 촉매의 대칭성에 따라 중합체의 입체 구조를 조절할 수 있으며, 이로부터 제조된 고분자는 분자량 분포가 좁고 공단량체의 분포가 균일하다는 장점을 갖는다.Such a metallocene catalyst is easy to copolymerize and can control the three-dimensional structure of the polymer according to the symmetry of the catalyst, and the polymer prepared therefrom has the advantage of having a narrow molecular weight distribution and uniform distribution of comonomers.
반면, 메탈로센 촉매에 의해 제조된 중합체는 좁은 분자량 분포로 인해 기계적 강도는 우수하나 가공성이 낮다는 단점을 갖는다. 이러한 단점을 해결하기 위해, 중합체의 분자 구조를 변경하거나 분자량 분포를 넓게 하는 등의 다양한 방법이 제시되었다. 예를 들어, 미국 특허 제5,272,236호에서는 중합체의 주사슬에 곁가지로 장쇄분지(long chain branch; LCB)를 도입시키는 촉매를 이용하여 중합체의 가공성을 개선시켰으나, 담지 촉매의 경우 활성이 낮은 문제점이 존재한다.On the other hand, the polymer prepared by the metallocene catalyst has a disadvantage in that it has excellent mechanical strength but low processability due to a narrow molecular weight distribution. In order to solve this disadvantage, various methods such as changing the molecular structure of the polymer or widening the molecular weight distribution have been proposed. For example, in US Patent No. 5,272,236, a catalyst for introducing a long chain branch (LCB) as a side branch to the main chain of the polymer is used to improve the processability of the polymer, but in the case of a supported catalyst, the activity is low. do.
이러한 단일 메탈로센 촉매의 단점을 해결하고, 보다 간편하게 활성이 우수하면서 가공성이 개선되는 촉매를 개발하기 위해, 서로 다른 특성을 가지는 메탈로센 촉매(이종 메탈로센 촉매)를 혼성 담지하는 방법이 제시되었다. 예를 들어, 미국 특허 제4,935,474호, 미국 특허 제6,828,394호, 미국 특허 제6,894,128호, 대한민국 특허 제1437509호, 미국 특허 제6,841,631호에는 공단량체에 대한 반응성이 서로 다른 촉매를 이용하여 이정(bimodal) 분자량 분포를 갖는 폴리올레핀을 제조하는 방법이 개시되어 있다. 이와 같은 방식으로 제조된 이정 분자량 분포를 갖는 폴리올레핀은 가공성은 향상되나 서로 다른 분자량 분포를 가짐으로 인해 동질성이 낮아진다. 따라서, 가공 후 균일한 물성을 갖는 제품을 얻기 어렵고 기계적 강도가 저하되는 문제점이 존재한다.In order to solve the shortcomings of such a single metallocene catalyst and to develop a catalyst having excellent activity and improved processability more conveniently, a method of hybridizing metallocene catalysts (heterogeneous metallocene catalysts) having different properties is proposed. presented For example, in U.S. Patent No. 4,935,474, U.S. Patent No. 6,828,394, U.S. Patent No. 6,894,128, Korean Patent No. 1437509, and U.S. Patent No. 6,841,631, a bimodal method using catalysts having different reactivity towards comonomers A method for preparing a polyolefin having a molecular weight distribution is disclosed. Polyolefins having a bimodal molecular weight distribution prepared in this way have improved processability, but have lower homogeneity due to having different molecular weight distributions. Therefore, there is a problem in that it is difficult to obtain a product having uniform physical properties after processing, and mechanical strength is lowered.
한편, 대한민국 특허 제1797890호에서는 브릿지로 연결되지 않은 씨클로펜타디에닐기와 인데닐기를 포함하는 제1 전이금속 화합물과 실릴 브릿지로 연결된 치환된 비스인데닐기를 포함하는 제2 전이금속 화합물을 혼합한 이종 메탈로센 촉매가 개시되어 있다.Meanwhile, in Korean Patent No. 1797890, a heterogeneous mixture of a first transition metal compound including a cyclopentadienyl group not connected by a bridge and an indenyl group and a second transition metal compound including a substituted bisindenyl group connected by a silyl bridge Metallocene catalysts are disclosed.
일반적으로, 이러한 혼성 촉매는 각각의 전이금속 화합물을 제조한 후 일정한 비로 섞어서 담지하는 방법으로 제조된다.In general, such a hybrid catalyst is prepared by preparing each transition metal compound and then mixing it in a constant ratio and supporting it.
본 발명의 목적은 중심 금속이 서로 다른 비다리형(non-bridged)의 비스사이클로펜타디에닐(biscyclopentadienyl; bisCp)기를 갖는 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 및 이를 포함하는 올레핀 중합용 촉매를 제공하는 것이다.An object of the present invention is a hybrid catalyst composition comprising a heterogeneous transition metal compound having a non-bridged biscyclopentadienyl (bisCp) group having a different central metal, and a catalyst for olefin polymerization comprising the same is to provide
본 발명의 다른 목적은 전이금속 화합물의 전구체 비율을 조절함으로써 혼성 촉매 조성물 및 이를 포함하는 올레핀 중합용 촉매를 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing a hybrid catalyst composition and a catalyst for olefin polymerization comprising the same by adjusting the precursor ratio of the transition metal compound.
본 발명의 목적을 달성하기 위한 일 구체예에 따라서, 아래 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 혼성 촉매 조성물이 제공된다.According to one embodiment for achieving the object of the present invention, there is provided a hybrid catalyst composition comprising a transition metal compound represented by Chemical Formulas 1 and 2 below.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 각각 독립적으로 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이고,In Formulas 1 and 2, M 1 and M 2 are different and each independently titanium (Ti), zirconium (Zr) or hafnium (Hf),
X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도, C6-20 아릴아미도 또는 C1-20 알킬리덴이며,each X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene;
R1 내지 R5와 R6 내지 R10은 각각 독립적으로 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이고, R1 내지 R5와 R6 내지 R10은 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있다.R 1 to R 5 and R 6 to R 10 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1 -20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl; R 1 to R 5 and R 6 to R 10 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.
바람직하게는, 위 화학식 1로 표시되는 화합물 대 위 화학식 2로 표시되는 화합물의 몰 비가 100:1~1:100의 범위이다.Preferably, the molar ratio of the compound represented by the above formula (1) to the compound represented by the above formula (2) is in the range of 100:1 to 1:100.
구체적으로, 본 발명의 구체예에 따른 혼성 촉매 조성물은 제1 혼성 촉매 조성물로서, 위 화학식 1과 화학식 2에서 M1과 M2가 서로 다르면서 각각 지르코늄 또는 하프늄이고, X가 각각 할로겐이며, R1 내지 R5와 R6 내지 R10이 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다. 더 구체적으로, 위 화학식 1과 화학식 2에서 X가 염소일 수 있다.Specifically, the hybrid catalyst composition according to an embodiment of the present invention is a first hybrid catalyst composition, wherein M 1 and M 2 are different from each other in Chemical Formulas 1 and 2, respectively, zirconium or hafnium, X is each halogen, R One to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl. More specifically, in Chemical Formulas 1 and 2, X may be chlorine.
또는, 본 발명의 구체예에 따른 혼성 촉매 조성물은 제2 혼성 촉매 조성물로서, 위 화학식 1과 화학식 2에서 M1과 M2가 서로 다르면서 각각 지르코늄 또는 하프늄이고, X가 각각 치환 또는 비치환된 C1-20 알킬이며, R1 내지 R5와 R6 내지 R10이 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다. 더 구체적으로, 위 화학식 1과 화학식 2에서 X가 메틸일 수 있다.Alternatively, the hybrid catalyst composition according to an embodiment of the present invention is a second hybrid catalyst composition, wherein M 1 and M 2 are different from each other in Chemical Formulas 1 and 2, respectively, zirconium or hafnium, and X is each substituted or unsubstituted C 1-20 alkyl, and R 1 to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl. More specifically, in Chemical Formulas 1 and 2, X may be methyl.
바람직하게는, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-1 내지 1-12로 표시되는 전이금속 화합물 중 적어도 하나이고, 위 화학식 2로 표시되는 전이금속 화합물이 아래 화학식 2-1 내지 2-12로 표시되는 전이금속 화합물 중 적어도 하나이다.Preferably, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-12 below, and the transition metal compound represented by Formula 2 is selected from Formulas 2-1 to 1-12 below. At least one of the transition metal compounds represented by 2-12.
[화학식 1-1] [화학식 1-2] [화학식 1-3][Formula 1-1] [Formula 1-2] [Formula 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6][Formula 1-4] [Formula 1-5] [Formula 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9][Formula 1-7] [Formula 1-8] [Formula 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12][Formula 1-10] [Formula 1-11] [Formula 1-12]
[화학식 2-1] [화학식 2-2] [화학식 2-3][Formula 2-1] [Formula 2-2] [Formula 2-3]
[화학식 2-4] [화학식 2-5] [화학식 2-6][Formula 2-4] [Formula 2-5] [Formula 2-6]
[화학식 2-7] [화학식 2-8] [화학식 2-9][Formula 2-7] [Formula 2-8] [Formula 2-9]
[화학식 2-10] [화학식 2-11] [화학식 2-12][Formula 2-10] [Formula 2-11] [Formula 2-12]
또는, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-13 내지 1-24로 표시되는 전이금속 화합물 중 적어도 하나이고, 위 화학식 2로 표시되는 전이금속 화합물이 아래 화학식 2-13 내지 2-24로 표시되는 전이금속 화합물 중 적어도 하나이다.Alternatively, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-13 to 1-24 below, and the transition metal compound represented by Formula 2 is represented by Formulas 2-13 to 2- At least one of the transition metal compounds represented by 24.
[화학식 1-13] [화학식 1-14] [화학식 1-15][Formula 1-13] [Formula 1-14] [Formula 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18][Formula 1-16] [Formula 1-17] [Formula 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21][Formula 1-19] [Formula 1-20] [Formula 1-21]
[화학식 1-22] [화학식 1-23] [화학식 1-24][Formula 1-22] [Formula 1-23] [Formula 1-24]
[화학식 2-13] [화학식 2-14] [화학식 2-15][Formula 2-13] [Formula 2-14] [Formula 2-15]
[화학식 2-16] [화학식 2-17] [화학식 2-18][Formula 2-16] [Formula 2-17] [Formula 2-18]
[화학식 2-19] [화학식 2-20] [화학식 2-21][Formula 2-19] [Formula 2-20] [Formula 2-21]
[화학식 2-22] [화학식 2-23] [화학식 2-24][Formula 2-22] [Formula 2-23] [Formula 2-24]
본 발명의 일 구체예에 따라서, (1) 아래 화학식 3으로 표시되는 화합물을 용매에 용해시키는 단계; (2) 단계 (1)에서 얻어진 용액에 아래 화학식 5로 표시되는 화합물을 첨가한 후 교반하에 반응시키는 단계; (3) 단계 (2)에서 얻어진 반응 혼합물에 아래 화학식 4로 표시되는 화합물과 아래 화학식 6으로 표시되는 화합물을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제1 혼성 촉매 조성물을 얻는 단계를 포함하되, 단계 (1)에서 첨가되는 화학식 3으로 표시되는 화합물 대 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물의 당량 비가 1:1~1.5:1이고, 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물 대 단계 (3)에서 첨가되는 화학식 6으로 표시되는 화합물의 당량 비가 1:100~100:1인, 혼성 촉매 조성물의 제조방법이 제공된다.According to one embodiment of the present invention, (1) dissolving the compound represented by the following formula (3) in a solvent; (2) adding a compound represented by the following formula (5) to the solution obtained in step (1), followed by reacting with stirring; (3) The compound represented by Formula 4 and the compound represented by Formula 6 below are added to the reaction mixture obtained in step (2) and reacted under stirring, including the transition metal compound represented by Formula 1 and Formula 2 An equivalent ratio of the compound represented by Formula 3 added in step (1) to the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1, including obtaining a first hybrid catalyst composition to and the equivalent ratio of the compound represented by Formula 5 added in step (2) to the compound represented by Formula 6 added in step (3) is 1:100 to 100:1, a method for preparing a hybrid catalyst composition is provided .
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
M1X4 M 1 X 4
[화학식 6][Formula 6]
M2X4 M 2 X 4
위 화학식 3 내지 6에서, X는 할로겐이고, M1, M2, R1 내지 R5와 R6 내지 R10은 위 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 항목에서 설명한 바와 같다.In Formulas 3 to 6, X is halogen, M 1 , M 2 , R 1 to R 5 and R 6 to R 10 are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.
바람직하게는, 위 단계 (1)에서, 위 화학식 3으로 표시되는 화합물이 아래 화학식 3-1 내지 3-6으로 표시되는 화합물 중 적어도 하나이다.Preferably, in the above step (1), the compound represented by Formula 3 is at least one of the compounds represented by Formulas 3-1 to 3-6 below.
[화학식 3-1] [화학식 3-2] [화학식 3-3][Formula 3-1] [Formula 3-2] [Formula 3-3]
[화학식 3-4] [화학식 3-5] [화학식 3-6][Formula 3-4] [Formula 3-5] [Formula 3-6]
위 단계 (1)에서, 용매가 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라히드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종을 포함할 수 있다.In the above step (1), the solvent may include at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate.
바람직하게는, 위 단계 (2)에서, 화학식 5로 표시되는 화합물이 ZrCl4이다.Preferably, in the above step (2), the compound represented by Formula 5 is ZrCl 4 .
위 단계 (2)에서 반응 온도가 0℃ 내지 120℃이고, 반응 시간이 1 내지 72시간이다.In the above step (2), the reaction temperature is 0° C. to 120° C., and the reaction time is 1 to 72 hours.
바람직하게는, 위 단계 (3)에서, 위 화학식 4로 표시되는 화합물이 아래 화학식 4-1 내지 4-12로 표시되는 화합물 중 적어도 하나이다.Preferably, in the above step (3), the compound represented by the above formula (4) is at least one of the compounds represented by the following formulas 4-1 to 4-12.
[화학식 4-1] [화학식 4-2] [화학식 4-3][Formula 4-1] [Formula 4-2] [Formula 4-3]
[화학식 4-4] [화학식 4-5] [화학식 4-6][Formula 4-4] [Formula 4-5] [Formula 4-6]
[화학식 4-7] [화학식 4-8] [화학식 4-9][Formula 4-7] [Formula 4-8] [Formula 4-9]
[화학식 4-10] [화학식 4-11] [화학식 4-12][Formula 4-10] [Formula 4-11] [Formula 4-12]
또한, 위 단계 (3)에서, 화학식 6으로 표시되는 화합물이 HfCl4이다.In addition, in the above step (3), the compound represented by Formula 6 is HfCl 4 .
위 단계 (3)에서 반응 온도가 0℃ 내지 120℃이고, 반응 시간이 1 내지 72시간이다.In the above step (3), the reaction temperature is 0° C. to 120° C., and the reaction time is 1 to 72 hours.
본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3a) 제1 혼성 촉매 조성물을 용매에 용해시키는 단계; 및 (3b) 단계 (3a)에서 얻어진 용액에 아래 화학식 7a로 표시되는 화합물, 화학식 7b로 표시되는 화합물 또는 불화수소암모늄(NH4HF2)을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제2 혼성 촉매 조성물을 얻는 단계를 추가로 포함할 수 있다.A method for preparing a hybrid catalyst composition according to an embodiment of the present invention comprises the steps of (3a) dissolving a first hybrid catalyst composition in a solvent; And (3b) to the solution obtained in step (3a), the compound represented by the formula 7a below, the compound represented by the formula 7b or ammonium hydrogen fluoride (NH 4 HF 2 ) is added and reacted under stirring, It may further include the step of obtaining a second hybrid catalyst composition comprising the transition metal compound represented by 2.
[화학식 7a][Formula 7a]
XaMgXb X a MgX b
[화학식 7b][Formula 7b]
XcLiX c Li
위 화학식 7a와 7b에서, Xa와 Xc는 각각 독립적으로 C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도, C6-20 아릴아미도 또는 C1-20 알킬리덴이고, Xb는 할로겐이다. 바람직하게는, 위 화학식 7a로 표시되는 화합물이 MeMgBr일 수 있고, 위 화학식 7b로 표시되는 화합물이 MeLi일 수 있다.In the above formulas 7a and 7b, X a and X c are each independently C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6- 20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene, and X b is halogen. Preferably, the compound represented by Formula 7a may be MeMgBr, and the compound represented by Formula 7b may be MeLi.
위 단계 (3a)에서, 용매가 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라히드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종을 포함할 수 있다.In the above step (3a), the solvent may include at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate.
바람직하게는, 위 단계 (b)에서 반응 온도가 0℃ 내지 120℃이고, 반응 시간이 1 내지 72시간이다.Preferably, in step (b), the reaction temperature is 0° C. to 120° C., and the reaction time is 1 to 72 hours.
본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3c) 제1 혼성 촉매 조성물 또는 제2 혼성 촉매 조성물을 건조시키는 단계를 추가로 포함할 수 있다.The method for preparing a hybrid catalyst composition according to an embodiment of the present invention may further include (3c) drying the first hybrid catalyst composition or the second hybrid catalyst composition.
또한, 본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3d) 단계 (3c)에서 건조된 제1 혼성 촉매 조성물 또는 제2 혼성 촉매 조성물을 용매에 용해시킨 후 필터로 미반응물 및/또는 불순물을 제거하는 단계를 추가로 포함할 수 있다.In addition, in the method for preparing a hybrid catalyst composition according to an embodiment of the present invention (3d), after dissolving the first hybrid catalyst composition or the second hybrid catalyst composition dried in step (3c) in a solvent, the unreacted material and / or The step of removing impurities may be further included.
위 단계 (3d)에서, 용매가 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라히드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종을 포함할 수 있다.In the above step (3d), the solvent may include at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate.
본 발명의 다른 목적을 달성하기 위한 일 구체예에 따라서, 제1 혼성 촉매 조성물 또는 제2 혼성 촉매 조성물; 및 조촉매 화합물을 포함하는 올레핀 중합용 촉매가 제공된다.According to one embodiment for achieving another object of the present invention, a first hybrid catalyst composition or a second hybrid catalyst composition; and a catalyst for olefin polymerization comprising a cocatalyst compound.
여기서, 조촉매 화합물은 아래 화학식 8로 표현되는 화합물, 화학식 9로 표현되는 화합물 및 화학식 10으로 표현되는 화합물로 구성되는 군으로부터 선택되는 하나 이상일 수 있다.Here, the promoter compound may be at least one selected from the group consisting of a compound represented by the following Chemical Formula 8, a compound represented by Chemical Formula 9, and a compound represented by Chemical Formula 10.
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]- [LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
위 화학식 8에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소기 또는 할로겐으로 치환된 C1-20 탄화수소기이고,In the above formula (8), n is an integer of 2 or more, R a is a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen,
위 화학식 9에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이며,In Chemical Formula 9, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a halogen-substituted C 1-20 hydrocarbon group. Or a C 1-20 alkoxy group,
위 화학식 10에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다.In the above formula (10), L is a neutral or cationic Lewis base, [LH] + and [L] + are a Bronsted acid, Z is a group 13 element, A is each independently substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group.
구체적으로, 위 화학식 8로 표시되는 화합물은 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산 및 부틸알루미녹산으로 구성되는 군으로부터 선택되는 적어도 하나이다.Specifically, the compound represented by Chemical Formula 8 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane.
또한, 화학식 9로 표시되는 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론 및 트리부틸보론으로 구성되는 군으로부터 선택되는 적어도 하나이다.In addition, the compound represented by Formula 9 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclopentylaluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron , at least one selected from the group consisting of triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron.
또한, 위 화학식 10으로 표시되는 화합물은 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리부틸암모니움테트라펜타플로로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플로로페닐보론, 디에틸암모니움테트라펜타플로로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리부틸암모니움테트라펜타플로로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플로로페닐알루미늄, 디에틸암모니움테트라펜타테트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라(p-트리플로로메틸페닐)보론 및 리페닐카보니움테트라펜타플로로페닐보론으로 구성되는 군으로부터 선택되는 적어도 하나이다.In addition, the compound represented by the above formula (10) is triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra ( p -tolyl) Boron, trimethylammonium tetra( o , p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, trimethylammonium tetra( p -trifluoromethylphenyl)boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra ( p -tolyl) ) Aluminum, tripropylammonium tetra( p -tolyl)aluminum, triethylammonium tetra( o , p -dimethylphenyl)aluminum, tributylammonium tetra( p -trifluoromethylphenyl)aluminum, trimethylammonium tetra( p -trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and rephenylcarboniumtetrapentafluorophenylboron selected from the group consisting of at least one
바람직하게는, 올레핀 중합용 촉매가 혼성 촉매 조성물을 담지하는 담체를 추가로 포함한다. 구체적으로, 담체가 혼성 촉매 조성물과 조촉매 화합물을 모두 담지할 수 있다.Preferably, the catalyst for olefin polymerization further comprises a carrier supporting the hybrid catalyst composition. Specifically, the carrier may support both the hybrid catalyst composition and the cocatalyst compound.
구체적으로, 위 담체는 실리카, 알루미나 및 마그네시아로 구성되는 군으로부터 선택되는 적어도 하나를 포함할 수 있다.Specifically, the carrier may include at least one selected from the group consisting of silica, alumina and magnesia.
여기서, 담체에 담지되는 혼성 전이금속 화합물의 총량이 담체 1 g을 기준으로 0.001~1 mmole이며, 담체에 담지되는 조촉매 화합물의 양이 담체 1 g을 기준으로 2~15 mmole이다.Here, the total amount of the hybrid transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier.
본 발명의 다른 구체예에 따라서, (1) 위 화학식 3으로 표시되는 화합물을 용매에 용해시키는 단계; (2) 단계 (1)에서 얻어진 용액에 위 화학식 5로 표시되는 화합물을 첨가한 후 교반하에 반응시키는 단계; (3) 단계 (2)에서 얻어진 반응 혼합물에 위 화학식 4로 표시되는 화합물과 위 화학식 6으로 표시되는 화합물을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제1 혼성 촉매 조성물을 얻는 단계; 및 (4) 혼성 촉매 조성물, 조촉매 화합물 또는 둘 다를 담체에 담지시키는 단계를 포함하되, 단계 (1)에서 첨가되는 화학식 3으로 표시되는 화합물 대 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물의 당량 비가 1:1~1.5:1이고, 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물 대 단계 (3)에서 첨가되는 화학식 6으로 표시되는 화합물의 당량 비가 1:100~100:1인, 올레핀 중합용 촉매의 제조방법이 제공된다.According to another embodiment of the present invention, (1) dissolving the compound represented by the above formula (3) in a solvent; (2) adding a compound represented by the above formula (5) to the solution obtained in step (1), followed by reacting with stirring; (3) The compound represented by Formula 4 and the compound represented by Formula 6 are added to the reaction mixture obtained in step (2), and then reacted under stirring to include the transition metal compound represented by Formula 1 and Formula 2 obtaining a first hybrid catalyst composition to and (4) supporting the hybrid catalyst composition, the cocatalyst compound, or both on a carrier, wherein the compound represented by Formula 3 added in step (1) vs. the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1, and the equivalent ratio of the compound represented by Formula 5 added in step (2) to the compound represented by Formula 6 added in step (3) is 1:100 to 100:1 , A method for preparing a catalyst for olefin polymerization is provided.
본 발명의 구체예에 따른 올레핀 중합용 촉매의 제조방법은 (3a) 제1 혼성 촉매 조성물을 용매에 용해시키는 단계; 및 (3b) 단계 (3a)에서 얻어진 용액에 위 화학식 7a로 표시되는 화합물, 화학식 7b로 표시되는 화합물 또는 불화수소암모늄(NH4HF2)을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제2 혼성 촉매 조성물을 얻는 단계를 추가로 포함할 수 있다.A method for preparing a catalyst for olefin polymerization according to an embodiment of the present invention comprises the steps of (3a) dissolving a first hybrid catalyst composition in a solvent; and (3b) the compound represented by Formula 7a, the compound represented by Formula 7b, or ammonium hydrogen fluoride (NH 4 HF 2 ) was added to the solution obtained in step (3a) and reacted under stirring, and the above Formula 1 and Formula 1 It may further include the step of obtaining a second hybrid catalyst composition comprising the transition metal compound represented by 2.
본 발명의 구체예에 따른 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 및 이를 포함하는 올레핀 중합용 촉매는 해당 전이금속 화합물의 함량에 따라서 우수한 가공성 및 기계적 물성을 갖는 폴리올레핀을 제조할 수 있다.The hybrid catalyst composition comprising a heterogeneous transition metal compound and the catalyst for olefin polymerization comprising the same according to an embodiment of the present invention can prepare polyolefins having excellent processability and mechanical properties depending on the content of the transition metal compound.
또한, 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 및 이를 포함하는 올레핀 중합용 촉매를 제조하는 방법은 혼성 전이금속 화합물의 비율을 정밀하게 조절함으로써, 우수한 가공성 및 기계적 물성을 갖는 폴리올레핀 중합용 촉매를 용이하게 제공할 수 있다.In addition, a hybrid catalyst composition comprising a heterogeneous transition metal compound and a method for preparing a catalyst for olefin polymerization comprising the same is a polyolefin polymerization catalyst having excellent processability and mechanical properties by precisely controlling the ratio of the mixed transition metal compound. can be provided easily.
이하, 본 발명에 관하여 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물Hybrid catalyst composition comprising heterogeneous transition metal compounds
본 발명의 일 구체예에 따라서, 아래 화학식 1과 2로 표시되는 전이금속 화합물을 포함하는 혼성 촉매 조성물이 제공된다.According to one embodiment of the present invention, there is provided a hybrid catalyst composition comprising a transition metal compound represented by Formulas 1 and 2 below.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이다. 구체적으로, M1과 M2는 서로 다르면서 지르코늄 또는 하프늄일 수 있다.In Formulas 1 and 2, M 1 and M 2 are different from each other and are titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M 1 and M 2 may be different from each other and may be zirconium or hafnium.
X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도, C6-20 아릴아미도 또는 C1-20 알킬리덴이다. 구체적으로, X는 각각 할로겐 또는 치환 또는 비치환된 C1-20 알킬일 수 있다.each X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene. Specifically, each X may be halogen or substituted or unsubstituted C 1-20 alkyl.
R1 내지 R5와 R6 내지 R10은 각각 독립적으로 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이다. 여기서, R1 내지 R5와 R6 내지 R10은 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있다. 구체적으로, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.R 1 to R 5 and R 6 to R 10 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1 -20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl. where R 1 to R 5 and R 6 to R 10 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring. Specifically, R 1 to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
본 발명의 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 화합물 대 위 화학식 2로 표시되는 화합물의 몰 비가 100:1~1:100의 범위일 수 있다. 바람직하게는, 이 두 화합물의 몰 비가 50:1~1:50이다. 더 바람직하게는, 이 두 화합물의 몰 비가 10:1~1:10이다.In a preferred embodiment of the present invention, the molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 above may be in the range of 100:1 to 1:100. Preferably, the molar ratio of these two compounds is from 50:1 to 1:50. More preferably, the molar ratio of these two compounds is 10:1 to 1:10.
본 발명의 바람직한 구체예에 있어서, 위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 각각 지르코늄 또는 하프늄이고, X는 각각 할로겐 또는 치환 또는 비치환된 C1-20 알킬이며, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.In a preferred embodiment of the present invention, in Formula 1 and Formula 2, M 1 and M 2 are different from each other and each represent zirconium or hafnium, X is halogen or substituted or unsubstituted C 1-20 alkyl, R One to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
구체적으로, 본 발명의 구체예에 따른 혼성 촉매 조성물이 제1 혼성 촉매 조성물일 수 있다. 이때, 위 화학식 1과 화학식 2에서 M1과 M2는 서로 다르면서 지르코늄 또는 하프늄이고, X는 각각 할로겐, 더 구체적으로 염소이며, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.Specifically, the hybrid catalyst composition according to an embodiment of the present invention may be the first hybrid catalyst composition. In this case, in Formulas 1 and 2, M 1 and M 2 are different from each other and are zirconium or hafnium, and X is each halogen, more specifically chlorine, and R 1 to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
또는, 본 발명의 구체예에 따른 혼성 촉매 조성물이 제2 혼성 촉매 조성물일 수 있다. 이때, 위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 지르코늄 또는 하프늄이고, X는 각각 치환 또는 비치환된 C1-20 알킬, 더 구체적으로 메틸이며, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.Alternatively, the hybrid catalyst composition according to an embodiment of the present invention may be the second hybrid catalyst composition. In this case, in Formulas 1 and 2, M 1 and M 2 are different from each other and are zirconium or hafnium, and X is each substituted or unsubstituted C 1-20 alkyl, more specifically methyl, and R 1 to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
본 발명의 더욱 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-1 내지 1-12로 표시되는 전이금속 화합물 중 적어도 하나이고, 위 화학식 2로 표시되는 전이금속 화합물이 아래 화학식 2-1 내지 2-12로 표시되는 전이금속 화합물 중 적어도 하나일 수 있다.In a more preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-12 below, and the transition metal compound represented by Formula 2 above is It may be at least one of the transition metal compounds represented by Formulas 2-1 to 2-12 below.
[화학식 1-1] [화학식 1-2] [화학식 1-3][Formula 1-1] [Formula 1-2] [Formula 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6][Formula 1-4] [Formula 1-5] [Formula 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9][Formula 1-7] [Formula 1-8] [Formula 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12][Formula 1-10] [Formula 1-11] [Formula 1-12]
[화학식 2-1] [화학식 2-2] [화학식 2-3][Formula 2-1] [Formula 2-2] [Formula 2-3]
[화학식 2-4] [화학식 2-5] [화학식 2-6][Formula 2-4] [Formula 2-5] [Formula 2-6]
[화학식 2-7] [화학식 2-8] [화학식 2-9][Formula 2-7] [Formula 2-8] [Formula 2-9]
[화학식 2-10] [화학식 2-11] [화학식 2-12][Formula 2-10] [Formula 2-11] [Formula 2-12]
또는, 본 발명의 더욱 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-13 내지 1-24로 표시되는 전이금속 화합물 중 적어도 하나이고, 위 화학식 2로 표시되는 전이금속 화합물이 아래 화학식 2-13 내지 2-24로 표시되는 전이금속 화합물 중 적어도 하나일 수 있다.Alternatively, in a more preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-13 to 1-24 below, and the transition metal represented by Formula 2 above The compound may be at least one of the transition metal compounds represented by Formulas 2-13 to 2-24 below.
[화학식 1-13] [화학식 1-14] [화학식 1-15][Formula 1-13] [Formula 1-14] [Formula 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18][Formula 1-16] [Formula 1-17] [Formula 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21][Formula 1-19] [Formula 1-20] [Formula 1-21]
[화학식 1-22] [화학식 1-23] [화학식 1-24][Formula 1-22] [Formula 1-23] [Formula 1-24]
[화학식 2-13] [화학식 2-14] [화학식 2-15][Formula 2-13] [Formula 2-14] [Formula 2-15]
[화학식 2-16] [화학식 2-17] [화학식 2-18][Formula 2-16] [Formula 2-17] [Formula 2-18]
[화학식 2-19] [화학식 2-20] [화학식 2-21][Formula 2-19] [Formula 2-20] [Formula 2-21]
[화학식 2-22] [화학식 2-23] [화학식 2-24][Formula 2-22] [Formula 2-23] [Formula 2-24]
혼성 촉매 조성물의 제조방법Method for preparing hybrid catalyst composition
(1) 아래 화학식 3으로 표시되는 화합물을 용매에 용해시키는 단계; (2) 단계 (1)에서 얻어진 용액에 아래 화학식 5로 표시되는 화합물을 첨가한 후 교반하에 반응시키는 단계; (3) 단계 (2)에서 얻어진 반응 혼합물에 아래 화학식 4로 표시되는 화합물과 아래 화학식 6으로 표시되는 화합물을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제1 혼성 촉매 조성물을 얻는 단계를 포함하되, 단계 (1)에서 첨가되는 화학식 3으로 표시되는 화합물 대 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물의 당량 비가 1:1~1.5:1이고, 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물 대 단계 (3)에서 첨가되는 화학식 6으로 표시되는 화합물의 당량 비가 1:100~100:1인, 혼성 촉매 조성물의 제조방법 이 제공된다.(1) dissolving the compound represented by Formula 3 below in a solvent; (2) adding a compound represented by the following formula (5) to the solution obtained in step (1), followed by reacting with stirring; (3) The compound represented by Formula 4 and the compound represented by Formula 6 below are added to the reaction mixture obtained in step (2) and reacted under stirring, including the transition metal compound represented by Formula 1 and Formula 2 An equivalent ratio of the compound represented by Formula 3 added in step (1) to the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1, including obtaining a first hybrid catalyst composition to and the equivalent ratio of the compound represented by Formula 5 added in step (2) to the compound represented by Formula 6 added in step (3) is 1:100 to 100:1, a method for preparing a hybrid catalyst composition is provided .
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
M1X4 M 1 X 4
[화학식 6][Formula 6]
M2X4 M 2 X 4
위 화학식 3 내지 6에서, X는 할로겐이고, M1, M2, R1 내지 R5와 R6 내지 R10은 위 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 항목에서 설명한 바와 같다.In Formulas 3 to 6, X is halogen, M 1 , M 2 , R 1 to R 5 and R 6 to R 10 are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.
단계 (1)Step (1)
구체적으로, 위 단계 (1)에서, 위 화학식 3으로 표시되는 화합물을 용매에 용해시킨다.Specifically, in the above step (1), the compound represented by the above formula (3) is dissolved in a solvent.
바람직하게는, 위 화학식 3으로 표시되는 화합물이 아래 화학식 3-1 내지 3-6으로 표시되는 화합물 중 적어도 하나이다.Preferably, the compound represented by Formula 3 above is at least one of the compounds represented by Formulas 3-1 to 3-6 below.
[화학식 3-1] [화학식 3-2] [화학식 3-3][Formula 3-1] [Formula 3-2] [Formula 3-3]
[화학식 3-4] [화학식 3-5] [화학식 3-6][Formula 3-4] [Formula 3-5] [Formula 3-6]
여기서, 용매는 헥산, 펜탄과 같은 지방족 탄화수소 용매, 톨루엔, 벤젠과 같은 방향족 탄화 수소 용매, 디클로로메탄과 같은 염소 원자로 치환된 탄화수소 용매, 디에틸에테르, 테트라히드로퓨란과 같은 에테르계 용매, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종을 포함할 수 있다. 바람직하게는, 위 용매가 톨루엔일 수 있으나, 이것으로 특별히 제한되지는 않는다.Here, the solvent is an aliphatic hydrocarbon solvent such as hexane and pentane, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an etheric solvent such as diethyl ether and tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate. Preferably, the above solvent may be toluene, but is not particularly limited thereto.
위 화학식 3으로 표시되는 화합물을 용매에 용해시킬 때, 온도와 용해 시간은 특별히 제한되지 않는다. 예를 들어, -78℃ 내지 80℃의 온도, 바람직하게는 -40℃ 내지 60℃의 온도, 더 바람직하게는 상온의 온도에서 위 화학식 3으로 표시되는 화합물을 용매에 첨가하고, 10분 내지 17시간, 바람직하게는 20분 내지 10시간, 더 바람직하게는 약 1시간 동안 이를 교반하여 용해시킬 수 있다.When the compound represented by Formula 3 above is dissolved in a solvent, the temperature and the dissolution time are not particularly limited. For example, the compound represented by the above formula 3 is added to the solvent at a temperature of -78°C to 80°C, preferably at a temperature of -40°C to 60°C, more preferably at room temperature, and 10 minutes to 17 minutes. Time, preferably 20 minutes to 10 hours, more preferably about 1 hour can be dissolved by stirring.
단계 (2)Step (2)
위 단계 (2)에서, 단계 (1)에서 얻어진 용액에 위 화학식 5로 표시되는 화합물을 첨가한 후 교반하에 반응시킨다.In the above step (2), the compound represented by the above formula (5) is added to the solution obtained in step (1), and then reacted under stirring.
바람직하게는, 위 화학식 5로 표시되는 화합물이 ZrCl4과 HfCl4 중에서 어느 하나일 수 있다. 더 바람직하게는, 위 화학식 5로 표시되는 화합물이 ZrCl4일 수 있다.Preferably, the compound represented by Formula 5 above may be any one of ZrCl 4 and HfCl 4 . More preferably, the compound represented by Formula 5 above may be ZrCl 4 .
화학식 5로 표시되는 화합물과 화학식을 첨가할 때의 온도는 -78℃ 내지 30℃의 범위인 것이 바람직하다. 더 바람직하게는, 화학식 5로 표시되는 화합물을 첨가할 때의 온도는 -40℃ 내지 10℃일 수 있다. 가장 바람직하게는, 화학식 5로 표시되는 화합물을 첨가할 때의 온도는 약 -30℃일 수 있다.The temperature at the time of adding the compound represented by the formula (5) and the formula is preferably in the range of -78°C to 30°C. More preferably, the temperature at which the compound represented by Formula 5 is added may be -40°C to 10°C. Most preferably, the temperature at which the compound represented by Formula 5 is added may be about -30°C.
화학식 5로 표시되는 화합물을 첨가한 후, 온도를 0℃ 내지 120℃의 범위, 더 바람직하게는 25℃ 내지 80℃의 범위, 가장 바람직하게는 약 65℃로 서서히 올려 1 내지 72시간, 바람직하게는 5 내지 48시간, 더 바람직하게는 12 내지 24시간 동안 교반하에 반응시킨다.After adding the compound represented by the formula (5), the temperature is gradually raised to a range of 0°C to 120°C, more preferably 25°C to 80°C, and most preferably about 65°C for 1 to 72 hours, preferably is reacted under stirring for 5 to 48 hours, more preferably 12 to 24 hours.
본 발명의 구체예에 따른 제조방법에 있어서, 단계 (1)에서 첨가되는 화학식 3으로 표시되는 화합물 대 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물의 당량 비가 1:1~1.5:1이다. 이 두 화합물의 당량 비는 바람직하게는 1.1:1~1.5:1, 더 바람직하게는 1.2:1~1.5:1이다. 이 경우, 화학식 1의 전이금속 화합물과는 다른 중심 금속을 갖는 화학식 2의 전이금속 화합물이 얻어질 수 있다.In the preparation method according to an embodiment of the present invention, the equivalent ratio of the compound represented by Formula 3 added in step (1) to the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1 . The equivalent ratio of these two compounds is preferably 1.1:1 to 1.5:1, more preferably 1.2:1 to 1.5:1. In this case, the transition metal compound of the formula (2) having a different central metal than the transition metal compound of the formula (1) can be obtained.
단계 (3)Step (3)
위 단계 (3)에서, 단계 (2)에서 얻어진 반응 혼합물에 위 화학식 4로 표시되는 화합물과 위 화학식 6으로 표시되는 화합물을 첨가한 후 교반하에 반응시킨다.In step (3), the compound represented by the above formula (4) and the compound represented by the above formula (6) are added to the reaction mixture obtained in step (2), and then reacted under stirring.
바람직하게는, 위 화학식 4로 표시되는 화합물이 아래 화학식 4-1 내지 4-12로 표시되는 화합물 중 적어도 하나일 수 있다.Preferably, the compound represented by Formula 4 may be at least one of the compounds represented by Formulas 4-1 to 4-12 below.
[화학식 4-1] [화학식 4-2] [화학식 4-3][Formula 4-1] [Formula 4-2] [Formula 4-3]
[화학식 4-4] [화학식 4-5] [화학식 4-6][Formula 4-4] [Formula 4-5] [Formula 4-6]
[화학식 4-7] [화학식 4-8] [화학식 4-9][Formula 4-7] [Formula 4-8] [Formula 4-9]
[화학식 4-10] [화학식 4-11] [화학식 4-12][Formula 4-10] [Formula 4-11] [Formula 4-12]
또한, 위 화학식 6으로 표시되는 화합물이 ZrCl4과 HfCl4 중에서 다른 하나일 수 있다. 바람직하게는, 위 화학식 6으로 표시되는 화합물이 HfCl4일 수 있다.In addition, the compound represented by Formula 6 above may be the other one of ZrCl 4 and HfCl 4 . Preferably, the compound represented by Formula 6 above may be HfCl 4 .
위 화학식 4로 표시되는 화합물과 위 화학식 6으로 표시되는 화합물을 첨가할 때의 온도는 -78℃ 내지 30℃의 범위인 것이 바람직하다. 더 바람직하게는, 위 화학식 4로 표시되는 화합물과 위 화학식 6으로 표시되는 화합물을 첨가할 때의 온도는 -40℃ 내지 10℃일 수 있다. 가장 바람직하게는, 위 화학식 4로 표시되는 화합물과 위 화학식 6으로 표시되는 화합물을 첨가할 때의 온도는 약 -30℃일 수 있다.When the compound represented by the above formula (4) and the compound represented by the above formula (6) are added, the temperature is preferably in the range of -78°C to 30°C. More preferably, the temperature when the compound represented by Formula 4 and the compound represented by Formula 6 are added may be -40°C to 10°C. Most preferably, the temperature when the compound represented by Formula 4 and the compound represented by Formula 6 are added may be about -30°C.
위 화학식 4로 표시되는 화합물과 위 화학식 6으로 표시되는 화합물을 첨가한 후, 온도를 0℃ 내지 120℃의 범위, 더 바람직하게는 0℃ 내지 60℃의 범위, 가장 바람직하게는 상온으로 서서히 올려 1 내지 72시간, 바람직하게는 3 내지 48시간, 더 바람직하게는 7 내지 22시간 동안 교반하에 반응시킨다.After adding the compound represented by the above formula 4 and the compound represented by the above formula 6, the temperature is gradually raised to a temperature in the range of 0°C to 120°C, more preferably in the range of 0°C to 60°C, and most preferably to room temperature. The reaction is carried out under stirring for 1 to 72 hours, preferably 3 to 48 hours, more preferably 7 to 22 hours.
단계 (3)에서, 위 화학식 1과 화학식 2에서 X가 할로겐인 제1 혼성 촉매 조성물이 얻어진다. 구체적으로, 위 화학식 1과 화학식 2에서 X가 염소인 제1 혼성 촉매 조성물이 얻어진다.In step (3), a first hybrid catalyst composition in which X is halogen in Chemical Formulas 1 and 2 is obtained. Specifically, in Chemical Formulas 1 and 2, a first hybrid catalyst composition in which X is chlorine is obtained.
본 발명의 구체예에 따른 제조방법에 있어서, 위 화학식 5로 표시되는 화합물 대 위 화학식 6으로 표시되는 화합물의 몰 비가 100:1~1:100의 범위일 수 있다. 바람직하게는, 이 두 화합물의 몰 비가 50:1~1:50이다. 더 바람직하게는, 이 두 화합물의 몰 비가 10:1~1:10이다.In the preparation method according to an embodiment of the present invention, the molar ratio of the compound represented by Formula 5 to the compound represented by Formula 6 above may be in the range of 100:1 to 1:100. Preferably, the molar ratio of these two compounds is from 50:1 to 1:50. More preferably, the molar ratio of these two compounds is 10:1 to 1:10.
본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3a) 제1 혼성 촉매 조성물을 용매에 단계; 및 (3b) 단계 (3a)에서 얻어진 용액에 아래 화학식 7a로 표시되는 화합물, 화학식 7b로 표시되는 화합물 또는 불화수소암모늄(NH4HF2)을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제2 혼성 촉매 조성물을 얻는 단계를 추가로 포함할 수 있다. 여기서, 아래 화학식 7a로 표시되는 화합물은 그리냐르(Grignard) 화합물일 수 있다.A method for preparing a hybrid catalyst composition according to an embodiment of the present invention comprises the steps of (3a) applying a first hybrid catalyst composition to a solvent; And (3b) to the solution obtained in step (3a), the compound represented by the formula 7a below, the compound represented by the formula 7b or ammonium hydrogen fluoride (NH 4 HF 2 ) is added and reacted under stirring, It may further include the step of obtaining a second hybrid catalyst composition comprising the transition metal compound represented by 2. Here, the compound represented by Chemical Formula 7a below may be a Grignard compound.
[화학식 7a][Formula 7a]
XaMgXb X a MgX b
[화학식 7b][Formula 7b]
XcLiX c Li
위 화학식 7a와 7b에서, Xa와 Xc는 각각 독립적으로 Xa는 C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도, C6-20 아릴아미도 또는 C1-20 알킬리덴이고, Xb는 할로겐일 수 있다. 바람직하게는, 위 화학식 7a로 표시되는 화합물이 MeMgBr일 수 있고, 위 화학식 7b로 표시되는 화합물이 MeLi일 수 있다.In the above formulas 7a and 7b, X a and X c are each independently X a is C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene, and X b may be halogen. Preferably, the compound represented by Formula 7a may be MeMgBr, and the compound represented by Formula 7b may be MeLi.
위 단계 (3a)에서, 제1 혼성 촉매 조성물을 용매에 용해시킨다.In the above step (3a), the first hybrid catalyst composition is dissolved in a solvent.
여기서, 용매는 위 단계 (1)에서 사용된 용매와 실질적으로 동일할 수 있다. 바람직하게는, 위 용매가 톨루엔일 수 있으나, 이것으로 특별히 제한되지는 않는다.Here, the solvent may be substantially the same as the solvent used in step (1) above. Preferably, the above solvent may be toluene, but is not particularly limited thereto.
위 단계 (3b)에서, 단계 (3a)에서 얻어진 용액에 위 화학식 7로 표시되는 화합물을 첨가한 후 교반하에 반응시킨다.In the above step (3b), the compound represented by the above formula (7) is added to the solution obtained in step (3a), and then reacted under stirring.
위 화학식 7로 표시되는 화합물을 첨가할 때의 온도는 -78℃ 내지 30℃의 범위인 것이 바람직하다. 더 바람직하게는, 화학식 7로 표시되는 화합물을 첨가할 때의 온도는 -40℃ 내지 10℃일 수 있다. 가장 바람직하게는, 화학식 7로 표시되는 화합물을 첨가할 때의 온도는 약 -30℃일 수 있다.The temperature when adding the compound represented by the above formula (7) is preferably in the range of -78 °C to 30 °C. More preferably, the temperature at which the compound represented by Formula 7 is added may be -40°C to 10°C. Most preferably, the temperature at which the compound represented by Formula 7 is added may be about -30°C.
위 화학식 7로 표시되는 화합물을 첨가한 후, 온도를 0℃ 내지 120℃의 범위, 더 바람직하게는 0℃ 내지 60℃의 범위, 가장 바람직하게는 상온으로 서서히 올려 1 내지 72시간, 바람직하게는 1 내지 24시간, 더 바람직하게는 약 3 내지 5시간 동안 교반하에 반응시킨다.After adding the compound represented by the above formula (7), the temperature is gradually raised to the range of 0 °C to 120 °C, more preferably in the range of 0 °C to 60 °C, most preferably to room temperature for 1 to 72 hours, preferably The reaction is carried out under stirring for 1 to 24 hours, more preferably about 3 to 5 hours.
위 단계 (3b)에서, 위 화학식 1과 화학식 2에서 X가 C1-20 알킬인 제2 혼성 촉매 조성물이 얻어진다. 구체적으로, 위 화학식 1과 화학식 2에서 X가 메틸인 제2 혼성 촉매 조성물이 얻어진다.In the above step (3b), a second hybrid catalyst composition in which X is C 1-20 alkyl in Formulas 1 and 2 is obtained. Specifically, a second hybrid catalyst composition in which X is methyl in Chemical Formulas 1 and 2 is obtained.
본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3c) 단계 (3)에서 얻어진 제1 혼성 촉매 조성물 또는 단계 (3b)에서 얻어진 제2 혼성 촉매 조성물을 건조시키는 단계를 추가로 포함할 수 있다. 여기서 조성물의 건조 조건은 특별히 제한되지는 않으나, 25℃ 내지 80℃의 온도 범위, 더 바람직하게는 25℃ 내지 50℃의 온도 범위, 가장 바람직하게는 약 25℃의 온도에서 수행할 수 있다.The method for preparing a hybrid catalyst composition according to an embodiment of the present invention may further include (3c) drying the first hybrid catalyst composition obtained in step (3) or the second hybrid catalyst composition obtained in step (3b). have. Here, the drying conditions of the composition are not particularly limited, but may be carried out in a temperature range of 25°C to 80°C, more preferably in a temperature range of 25°C to 50°C, and most preferably at a temperature of about 25°C.
또한, 본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3d) 위 단계 (3c)에서 건조된 제1 혼성 촉매 조성물 또는 제2 혼성 촉매 조성물을 용매에 용해시킨 후 필터로 미반응물 및/또는 불순물을 제거하는 단계를 추가로 포함할 수 있다. 여기서, 용매는 위 단계 (1)에서 사용된 용매와 실질적으로 동일할 수 있다. 바람직하게는, 디클로로메탄이 사용될 수 있으나, 이것으로 제한되는 것은 아니다. 미반응물 및/또는 불순물을 제거하는 필터는 특별히 제한되지는 않으나, 셀라이트 필터를 사용하는 것이 바람직하다.In addition, in the method for preparing a hybrid catalyst composition according to an embodiment of the present invention (3d), the first hybrid catalyst composition or the second hybrid catalyst composition dried in step (3c) is dissolved in a solvent, and then the unreacted material and / Alternatively, the step of removing impurities may be further included. Here, the solvent may be substantially the same as the solvent used in step (1) above. Preferably, dichloromethane can be used, but is not limited thereto. The filter for removing unreacted substances and/or impurities is not particularly limited, but it is preferable to use a Celite filter.
올레핀 중합용 촉매Catalyst for Olefin Polymerization
본 발명의 다른 구체예에 따라서, 아래 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 혼성 촉매 조성물; 및 조촉매 화합물을 포함하는 올레핀 중합용 촉매가 제공된다.According to another embodiment of the present invention, a hybrid catalyst composition comprising a transition metal compound represented by Formula 1 and Formula 2 below; and a catalyst for olefin polymerization comprising a cocatalyst compound.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
위 화학식 1과 2에서, M1, M2, X, R1 내지 R5와 R6 내지 R10은 위 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 항목에서 설명한 바와 같다.In Formulas 1 and 2 above, M 1 , M 2 , X, R 1 to R 5 and R 6 to R 10 are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.
본 발명의 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 화합물 대 위 화학식 2로 표시되는 화합물의 몰 비가 100:1~1:100의 범위일 수 있다. 바람직하게는, 이 두 화합물의 몰 비가 50:1~1:50이다. 더 바람직하게는, 이 두 화합물의 몰 비가 10:1~1:10이다.In a preferred embodiment of the present invention, the molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 above may be in the range of 100:1 to 1:100. Preferably, the molar ratio of these two compounds is from 50:1 to 1:50. More preferably, the molar ratio of these two compounds is 10:1 to 1:10.
본 발명의 바람직한 구체예에 있어서, 위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 각각 지르코늄 또는 하프늄이고, X는 각각 할로겐 또는 치환 또는 비치환된 C1-20 알킬이며, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.In a preferred embodiment of the present invention, in Formula 1 and Formula 2, M 1 and M 2 are different from each other and each represent zirconium or hafnium, X is halogen or substituted or unsubstituted C 1-20 alkyl, R One to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
구체적으로, 본 발명의 구체예에 따른 올레핀 중합용 촉매는 제1 혼성 촉매 조성물을 포함할 수 있다. 이때, 위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 지르코늄 또는 하프늄이고, X는 각각 할로겐, 더 구체적으로 염소이며, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.Specifically, the catalyst for olefin polymerization according to an embodiment of the present invention may include a first hybrid catalyst composition. In this case, in Chemical Formulas 1 and 2, M 1 and M 2 are different from each other and are zirconium or hafnium, X is each halogen, more specifically chlorine, and R 1 to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
또는, 본 발명의 구체예에 따른 올레핀 중합용 촉매는 제2 혼성 촉매 조성물을 포함할 수 있다. 이때, 위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 지르코늄 또는 하프늄이고, X는 각각 치환 또는 비치환된 C1-20 알킬, 더 구체적으로 메틸이며, R1 내지 R5와 R6 내지 R10은 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.Alternatively, the catalyst for olefin polymerization according to an embodiment of the present invention may include a second hybrid catalyst composition. In this case, in Formulas 1 and 2, M 1 and M 2 are different from each other and are zirconium or hafnium, and X is each substituted or unsubstituted C 1-20 alkyl, more specifically methyl, and R 1 to R 5 and R 6 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
본 발명의 더욱 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-1 내지 1-12로 표시되는 전이금속 화합물 중 적어도 하나이고, 위 화학식 2로 표시되는 전이금속 화합물이 아래 화학식 2-1 내지 2-12로 표시되는 전이금속 화합물 중 적어도 하나일 수 있다.In a more preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-12 below, and the transition metal compound represented by Formula 2 above is It may be at least one of the transition metal compounds represented by Formulas 2-1 to 2-12 below.
[화학식 1-1] [화학식 1-2] [화학식 1-3][Formula 1-1] [Formula 1-2] [Formula 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6][Formula 1-4] [Formula 1-5] [Formula 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9][Formula 1-7] [Formula 1-8] [Formula 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12][Formula 1-10] [Formula 1-11] [Formula 1-12]
[화학식 2-1] [화학식 2-2] [화학식 2-3][Formula 2-1] [Formula 2-2] [Formula 2-3]
[화학식 2-4] [화학식 2-5] [화학식 2-6][Formula 2-4] [Formula 2-5] [Formula 2-6]
[화학식 2-7] [화학식 2-8] [화학식 2-9][Formula 2-7] [Formula 2-8] [Formula 2-9]
[화학식 2-10] [화학식 2-11] [화학식 2-12][Formula 2-10] [Formula 2-11] [Formula 2-12]
또는, 본 발명의 더욱 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-13 내지 1-24로 표시되는 전이금속 화합물 중 적어도 하나이고, 위 화학식 2로 표시되는 전이금속 화합물이 아래 화학식 2-13 내지 2-24로 표시되는 전이금속 화합물 중 적어도 하나이다.Alternatively, in a more preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-13 to 1-24 below, and the transition metal represented by Formula 2 above The compound is at least one of the transition metal compounds represented by Formulas 2-13 to 2-24 below.
[화학식 1-13] [화학식 1-14] [화학식 1-15][Formula 1-13] [Formula 1-14] [Formula 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18][Formula 1-16] [Formula 1-17] [Formula 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21][Formula 1-19] [Formula 1-20] [Formula 1-21]
[화학식 1-22] [화학식 1-23] [화학식 1-24][Formula 1-22] [Formula 1-23] [Formula 1-24]
[화학식 2-13] [화학식 2-14] [화학식 2-15][Formula 2-13] [Formula 2-14] [Formula 2-15]
[화학식 2-16] [화학식 2-17] [화학식 2-18][Formula 2-16] [Formula 2-17] [Formula 2-18]
[화학식 2-19] [화학식 2-20] [화학식 2-21][Formula 2-19] [Formula 2-20] [Formula 2-21]
[화학식 2-22] [화학식 2-23] [화학식 2-24][Formula 2-22] [Formula 2-23] [Formula 2-24]
한편, 조촉매 화합물은 아래 화학식 8로 표현되는 화합물, 화학식 9로 표현되는 화합물 및 화학식 10으로 표현되는 화합물 중 하나 이상을 포함할 수 있다.Meanwhile, the cocatalyst compound may include at least one of a compound represented by the following Chemical Formula 8, a compound represented by Chemical Formula 9, and a compound represented by Chemical Formula 10.
[화학식 8][Formula 8]
위 화학식 8에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소 또는 할로겐으로 치환된 C1-20 탄화수소일 수 있다. 구체적으로, Ra는 메틸, 에틸, n-부틸 또는 이소부틸일 수 있다.In Formula 8, n is an integer of 2 or more, and R a may be a halogen atom, a C 1-20 hydrocarbon, or a halogen-substituted C 1-20 hydrocarbon. Specifically, R a may be methyl, ethyl, n -butyl or isobutyl.
[화학식 9][Formula 9]
위 화학식 9에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이다. 구체적으로, D가 알루미늄(Al)일 때, Rb, Rc 및 Rd는 각각 독립적으로 메틸 또는 이소부틸일 수 있고, D가 보론(B)일 때, Rb, Rc 및 Rd는 각각 펜타플루오로페닐일 수 있다.In Chemical Formula 9, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a halogen-substituted C 1-20 hydrocarbon group. or a C 1-20 alkoxy group. Specifically, when D is aluminum (Al), R b , R c and R d may each independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d are each may be pentafluorophenyl.
[화학식 10][Formula 10]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]- [LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
위 화학식 10에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다. 구체적으로, [L-H]+는 디메틸아닐리늄 양이온일 수 있고, [Z(A)4]-는 [B(C6F5)4]-일 수 있으며, [L]+는 [(C6H5)3C]+일 수 있다.In the above formula (10), L is a neutral or cationic Lewis base, [LH] + and [L] + are a Bronsted acid, Z is a group 13 element, A is each independently substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group. Specifically, [LH] + may be a dimethylanilinium cation, [Z(A) 4 ] - may be [B(C 6 F 5 ) 4 ] - , [L] + may be [(C 6 H) 5 ) 3 C] + .
구체적으로, 위 화학식 8로 표시되는 화합물의 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등을 들 수 있으며, 메틸알루미녹산이 바람직하나, 이들로 제한되는 것은 아니다.Specifically, examples of the compound represented by the above formula (8) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferable, but is not limited thereto.
위 화학식 9로 표시되는 화합물의 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등을 들 수 있으며, 트리메틸알루미늄, 트리에틸알루미늄 및 트리이소부틸알루미늄이 바람직하나, 이들로 제한되는 것은 아니다.Examples of the compound represented by the above formula (9) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and trimethylaluminum, triethylaluminum and triisobutylaluminum are preferred, but are not limited thereto.
위 화학식 10으로 표시되는 화합물의 예로는 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리부틸암모니움테트라펜타플로로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플로로페닐보론, 디에틸암모니움테트라펜타플로로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리부틸암모니움테트라펜타플로로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플로로페닐알루미늄, 디에틸암모니움테트라펜타테트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라(p-트리플로로메틸페닐)보론, 리페닐카보니움테트라펜타플로로페닐보론 등을 들 수 있다.Examples of the compound represented by the above formula (10) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra( p -tolyl) Boron, trimethylammonium tetra( o , p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, trimethylammonium tetra( p -trifluoromethylphenyl)boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra ( p -tolyl) ) Aluminum, tripropylammonium tetra( p -tolyl)aluminum, triethylammonium tetra( o , p -dimethylphenyl)aluminum, tributylammonium tetra( p -trifluoromethylphenyl)aluminum, trimethylammonium tetra( p -trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron, and rephenylcarboniumtetrapentafluorophenylboron.
본 발명의 바람직한 구체예에 있어서, 올레핀 중합용 촉매가 혼성 촉매 조성물을 담지하는 담체를 추가로 포함할 수 있다. 구체적으로, 담체가 혼성 촉매 조성물과 조촉매 화합물을 모두 담지할 수 있다.In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting the hybrid catalyst composition. Specifically, the carrier may support both the hybrid catalyst composition and the cocatalyst compound.
이때, 담체는 표면에 히드록시기를 함유하는 물질을 포함할 수 있으며, 바람직하게는 건조되어 표면에 수분이 제거된, 반응성이 큰 히드록시기와 실록산기를 갖는 물질이 사용될 수 있다. 예컨대, 담체는 실리카, 알루미나 및 마그네시아로 구성되는 군으로부터 선택되는 적어도 하나를 포함할 수 있다. 구체적으로, 고온에서 건조된 실리카, 실리카-알루미나, 및 실리카-마그네시아 등이 담체로서 사용될 수 있고, 이들은 통상적으로 Na2O, K2CO3, BaSO4, 및 Mg(NO3)2 등의 산화물, 탄산염, 황산염, 및 질산염 성분을 함유할 수 있다. 또한, 이들은 탄소, 제올라이트, 염화 마그네슘 등을 포함할 수도 있다. 다만, 담체가 이들로 제한되는 것은 아니며, 전이금속 화합물과 조촉매 화합물을 담지할 수 있는 것이면 특별히 제한되지 않는다.In this case, the carrier may include a material containing a hydroxyl group on the surface, preferably dried to remove moisture from the surface, a material having a high reactivity hydroxyl group and siloxane group may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina and magnesia. Specifically, silica dried at high temperature, silica-alumina, silica-magnesia, and the like may be used as the carrier, and these are typically oxides such as Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) 2 . , carbonate, sulfate, and nitrate components. They may also contain carbon, zeolites, magnesium chloride, and the like. However, the carrier is not limited thereto, and is not particularly limited as long as it can support the transition metal compound and the promoter compound.
담체는 평균 입도가 10~250 ㎛일 수 있으며, 바람직하게는 평균 입도가 10~150 ㎛일 수 있고, 보다 바람직하게는 20~100 ㎛일 수 있다.The carrier may have an average particle size of 10-250 μm, preferably an average particle size of 10-150 μm, and more preferably 20-100 μm.
담체의 미세기공 부피는 0.1~10 cc/g일 수 있으며, 바람직하게는 0.5~5 cc/g일 수 있고, 보다 바람직하게는 1.0~3.0 cc/g일 수 있다.The micropore volume of the carrier may be 0.1-10 cc/g, preferably 0.5-5 cc/g, and more preferably 1.0-3.0 cc/g.
담체의 비표면적은 1~1,000 ㎡/g일 수 있으며, 바람직하게는 100~800 ㎡/g일 수 있고, 보다 바람직하게는 200~600 ㎡/g일 수 있다.The specific surface area of the carrier may be 1 to 1,000 m2/g, preferably 100 to 800 m2/g, and more preferably 200 to 600 m2/g.
바람직한 일 실시예에서, 담체가 실리카일 경우, 실리카는 건조 온도는 상온~900℃일 수 있다. 건조 온도는 바람직하게는 상온~800℃, 보다 바람직하게는 상온~700℃일 수 있다. 건조 온도가 상온보다 낮을 경우에는 수분이 너무 많아서 표면의 수분과 조촉매가 반응하게 되고, 900℃를 초과하게 되면 담체의 구조가 붕괴될 수 있다.In a preferred embodiment, when the carrier is silica, the silica drying temperature may be room temperature ~ 900 ℃. The drying temperature may be preferably from room temperature to 800°C, more preferably from room temperature to 700°C. When the drying temperature is lower than room temperature, there is too much moisture, so that the surface moisture and the cocatalyst react, and when it exceeds 900° C., the structure of the carrier may collapse.
건조된 실리카 내의 히드록시기의 농도는 0.1~5 mmole/g일 수 있으며, 바람직하게는 0.7~4 mmole/g일 수 있고, 보다 바람직하게는 1.0~2 mmole/g일 수 있다. 히드록시기의 농도가 0.1 mmole/g 미만이면 조촉매의 담지량이 낮아지며, 5 mmole/g을 초과하면 촉매 성분이 불활성화되는 문제점이 발생할 수 있다.The concentration of hydroxyl groups in the dried silica may be 0.1-5 mmole/g, preferably 0.7-4 mmole/g, and more preferably 1.0-2 mmole/g. When the concentration of the hydroxyl group is less than 0.1 mmole/g, the supported amount of the cocatalyst is lowered, and when it exceeds 5 mmole/g, a problem in that the catalyst component is deactivated may occur.
담체에 담지되는 혼성 전이금속 화합물의 총량은 담체 1 g을 기준으로 0.001~1 mmole일 수 있다. 혼성 전이금속 화합물과 담체의 비가 위 범위를 만족하면, 적절한 담지 촉매 활성을 나타내어 촉매의 활성 유지 및 경제성 측면에서 유리하다.The total amount of the hybrid transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier. When the ratio of the hybrid transition metal compound to the carrier satisfies the above range, an appropriate supported catalyst activity is exhibited, which is advantageous in terms of maintaining the activity of the catalyst and economic feasibility.
담체에 담지되는 조촉매 화합물의 양은 담체 1 g을 기준으로 2~15 mmole일 수 있다. 조촉매 화합물과 담체의 비가 위 범위를 만족하면, 촉매의 활성 유지 및 경제성 측면에서 유리하다.The amount of the promoter compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier. When the ratio of the promoter compound and the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economic feasibility.
담체는 1종 또는 2종 이상이 사용될 수 있다. 예를 들어, 1종의 담체에 혼성 촉매 조성물과 조촉매 화합물이 모두 담지될 수도 있고, 2종 이상의 담체에 혼성 촉매 조성물과 조촉매 화합물이 각각 담지될 수도 있다. 또한, 혼성 촉매 조성물과 조촉매 화합물 중 하나만이 담체에 담지될 수도 있다.One type or two or more types of carriers may be used. For example, both the hybrid catalyst composition and the promoter compound may be supported on one type of support, or the hybrid catalyst composition and the promoter compound may be supported on two or more types of support, respectively. In addition, only one of the hybrid catalyst composition and the cocatalyst compound may be supported on the carrier.
올레핀 중합용 촉매의 제조방법Method for preparing catalyst for olefin polymerization
본 발명의 다른 구체예에 따라서, (1) 아래 화학식 3으로 표시되는 화합물을 용매에 용해시키는 단계; (2) 단계 (1)에서 얻어진 용액에 아래 화학식 5로 표시되는 화합물을 첨가한 후 교반하에 반응시키는 단계; (3) 단계 (2)에서 얻어진 반응 혼합물에 아래 화학식 4로 표시되는 화합물과 아래 화학식 6으로 표시되는 화합물을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제1 혼성 촉매 조성물을 얻는 단계; 및 (4) 혼성 촉매 조성물, 조촉매 화합물 또는 둘 다를 담체에 담지시키는 단계를 포함하되, 단계 (1)에서 첨가되는 화학식 3으로 표시되는 화합물 대 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물의 당량 비가 1:1~1.5:1이고, 단계 (2)에서 첨가되는 화학식 5로 표시되는 화합물 대 단계 (3)에서 첨가되는 화학식 6으로 표시되는 화합물의 당량 비가 1:100~100:1인, 올레핀 중합용 촉매의 제조방법 이 제공된다.According to another embodiment of the present invention, (1) dissolving a compound represented by Formula 3 below in a solvent; (2) adding a compound represented by the following formula (5) to the solution obtained in step (1), followed by reacting with stirring; (3) The compound represented by Formula 4 and the compound represented by Formula 6 below are added to the reaction mixture obtained in step (2) and reacted under stirring, including the transition metal compound represented by Formula 1 and Formula 2 obtaining a first hybrid catalyst composition to and (4) supporting the hybrid catalyst composition, the cocatalyst compound, or both on a carrier, wherein the compound represented by Formula 3 added in step (1) vs. the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1, and the equivalent ratio of the compound represented by Formula 5 added in step (2) to the compound represented by Formula 6 added in step (3) is 1:100 to 100:1 , a method for preparing a catalyst for olefin polymerization is provided.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
M1X4 M 1 X 4
[화학식 6][Formula 6]
M2X4 M 2 X 4
위 화학식 1 내지 6에서, X는 할로겐이고, M1, M2, R1 내지 R5와 R6 내지 R10은 위 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 항목에서 설명한 바와 같다.In Formulas 1 to 6, X is halogen, M 1 , M 2 , R 1 to R 5 and R 6 to R 10 are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.
위 단계 (1) 내지 단계 (3)의 구체적인 내용은 위 혼성 촉매 조성물의 제조방법의 단계 (1) 내지 단계 (3)과 실질적으로 동일하다.Specific details of steps (1) to (3) are substantially the same as steps (1) to (3) of the method for preparing the hybrid catalyst composition.
본 발명의 구체예에 따른 올레핀 중합용 촉매의 제조방법은 (3a) 제1 혼성 촉매 조성물을 용매에 단계; 및 (3b) 단계 (3a)에서 얻어진 용액에 아래 화학식 7a로 표시되는 화합물, 화학식 7b로 표시되는 화합물 또는 불화수소암모늄(NH4HF2)을 첨가한 후 교반하에 반응시켜, 위 화학식 1과 화학식 2로 표시되는 전이금속 화합물을 포함하는 제2 혼성 촉매 조성물을 얻는 단계를 추가로 포함할 수 있다.A method for preparing a catalyst for olefin polymerization according to an embodiment of the present invention comprises the steps of (3a) applying a first hybrid catalyst composition to a solvent; And (3b) to the solution obtained in step (3a), the compound represented by the formula 7a below, the compound represented by the formula 7b or ammonium hydrogen fluoride (NH 4 HF 2 ) is added and reacted under stirring, It may further include the step of obtaining a second hybrid catalyst composition comprising the transition metal compound represented by 2.
[화학식 7a][Formula 7a]
XaMgXb X a MgX b
[화학식 7b][Formula 7b]
XcLiX c Li
위 화학식 7a와 7b에서, Xa, Xb 및 Xc는 위 혼성 촉매 조성물의 제조방법 항목에서 설명한 바와 같다.In Formulas 7a and 7b, X a , X b and X c are the same as described in the section on the method for preparing the hybrid catalyst composition.
위 단계 (3a) 및 단계 (3b)의 구체적인 내용은 위 혼성 촉매 조성물의 제조방법의 단계 (3a) 및 단계 (3b)와 실질적으로 동일하다.Specific details of steps (3a) and (3b) are substantially the same as steps (3a) and (3b) of the above method for preparing the hybrid catalyst composition.
본 발명의 다른 구체예에 따른 올레핀 중합용 촉매의 제조방법은 (3c) 단계 (3)에서 얻어진 제1 혼성 촉매 조성물 또는 단계 (3b)에서 얻어진 제2 혼성 촉매 조성물을 건조시키는 단계를 추가로 포함할 수 있다. 이때, 위 단계 (3c)의 구체적인 내용은 위 혼성 촉매 조성물의 제조방법의 단계 (3c)와 실질적으로 동일하다.The method for preparing a catalyst for olefin polymerization according to another embodiment of the present invention further comprises (3c) drying the first hybrid catalyst composition obtained in step (3) or the second hybrid catalyst composition obtained in step (3b) can do. In this case, the specific details of step (3c) are substantially the same as step (3c) of the method for preparing the hybrid catalyst composition.
또한, 본 발명의 구체예에 따른 혼성 촉매 조성물의 제조방법은 (3d) 단계 (3c)에서 건조된 제1 혼성 촉매 조성물 또는 제2 혼성 촉매 조성물을 용매에 용해시킨 후 필터로 미반응물 및/또는 불순물을 제거하는 단계를 추가로 포함할 수 있다. 이때, 위 단계 (3d)의 구체적인 내용은 위 혼성 촉매 조성물의 제조방법의 단계 (3d)와 실질적으로 동일하다.In addition, in the method for preparing a hybrid catalyst composition according to an embodiment of the present invention (3d), after dissolving the first hybrid catalyst composition or the second hybrid catalyst composition dried in step (3c) in a solvent, the unreacted material and / or The step of removing impurities may be further included. In this case, the specific content of the step (3d) is substantially the same as the step (3d) of the method for preparing the hybrid catalyst composition.
단계 (4)Step (4)
위 단계 (4)에서, 혼성 촉매 조성물, 조촉매 화합물 또는 둘 다를 담체에 담지시킨다.In the above step (4), the hybrid catalyst composition, the cocatalyst compound, or both are supported on a carrier.
혼성 촉매 조성물 및/또는 조촉매 화합물을 담지하는 방법으로서, 물리적 흡착 방법 또는 화학적 흡착 방법이 사용될 수 있다.As a method for supporting the hybrid catalyst composition and/or the cocatalyst compound, a physical adsorption method or a chemical adsorption method may be used.
예를 들어, 물리적 흡착 방법은 혼성 촉매 조성물이 용해된 용액을 담체에 접촉시킨 후 건조하는 방법, 혼성 촉매 조성물과 조촉매 화합물이 용해된 용액을 담체에 접촉시킨 후 건조하는 방법, 또는 혼성 촉매 조성물이 용해된 용액을 담체에 접촉시킨 후 건조하여 혼성 촉매 조성물이 담지된 담체를 제조하고, 이와 별개로 조촉매 화합물이 용해된 용액을 담체에 접촉시킨 후 건조하여 조촉매 화합물이 담지된 담체를 제조한 후, 이들을 혼합하는 방법 등일 수 있다.For example, the physical adsorption method is a method of drying a solution in which the hybrid catalyst composition is dissolved in contact with a carrier and then drying, a method in which a solution in which the hybrid catalyst composition and a cocatalyst compound are dissolved is contacted with a carrier and then drying, or a hybrid catalyst composition The dissolved solution is brought into contact with the carrier and dried to prepare a carrier on which the hybrid catalyst composition is supported. Separately, a solution in which the cocatalyst compound is dissolved is contacted with the carrier and dried to prepare a carrier on which the cocatalyst compound is supported. After that, it may be a method of mixing them, or the like.
화학적 흡착 방법은 담체의 표면에 조촉매 화합물을 먼저 담지시킨 후, 조촉매 화합물에 혼성 촉매 조성물을 담지시키는 방법, 또는 담체의 표면의 작용기(예를 들어, 실리카의 경우 실리카 표면의 히드록시기(-OH))와 혼성 전이금속 화합물을 공유결합시키는 방법 등일 수 있다.The chemical adsorption method is a method in which a promoter compound is first supported on the surface of a carrier, and then a hybrid catalyst composition is supported on the promoter compound, or a functional group on the surface of the support (for example, in the case of silica, a hydroxyl group on the silica surface (-OH) )) and a method of covalently bonding a hybrid transition metal compound, and the like.
여기서, 혼성 촉매 조성물 및/또는 조촉매 화합물을 담지시킬 때 사용되는 용매는 특별히 제한되지 않는다. 예를 들어, 용매는 헥산, 펜탄과 같은 지방족 탄화수소 용매, 톨루엔, 벤젠과 같은 방향족 탄화 수소 용매, 디클로로메탄과 같은 염소 원자로 치환된 탄화수소 용매, 디에틸에테르, 테트라히드로퓨란과 같은 에테르계 용매, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종을 포함할 수 있다.Here, the solvent used for supporting the hybrid catalyst composition and/or the cocatalyst compound is not particularly limited. For example, the solvent may be an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an etheric solvent such as diethyl ether or tetrahydrofuran, acetone And it may include at least one selected from the group consisting of ethyl acetate.
바람직한 일 실시예에서, 위 단계 (4)에서 담체에 혼성 촉매 조성물 및/또는 조촉매 화합물을 담지시키는 과정은 0~100℃의 온도, 바람직하게는 실온~90℃의 온도에서 수행될 수 있다.In a preferred embodiment, the process of supporting the hybrid catalyst composition and/or the cocatalyst compound on the carrier in step (4) above may be performed at a temperature of 0 to 100°C, preferably at a temperature of room temperature to 90°C.
또한, 단계 (4)에서 담체에 혼성 촉매 조성물 및/또는 조촉매 화합물을 담지시키는 과정은 혼성 촉매 조성물 및/또는 조촉매 화합물과 담체의 혼합물을 1분~24시간, 바람직하게는 5분~15시간 동안 충분히 교반함으로써 수행될 수 있다.In addition, the process of supporting the hybrid catalyst composition and/or the promoter compound on the carrier in step (4) is a mixture of the hybrid catalyst composition and/or the promoter compound and the carrier for 1 minute to 24 hours, preferably 5 minutes to 15 minutes. It can be carried out by sufficiently stirring for a period of time.
올레핀의 중합polymerization of olefins
본 발명의 구체예에 따른 올레핀 중합용 촉매의 존재 하에 올레핀계 단량체를 중합하여 올레핀계 중합체를 제조할 수 있다.An olefin-based polymer may be prepared by polymerizing an olefin-based monomer in the presence of a catalyst for olefin polymerization according to an embodiment of the present invention.
여기서, 올레핀계 중합체는 올레핀계 단량체의 단독 중합체(homopolymer) 또는 올레핀계 단량체와 공단량체의 공중합체(copolymer)일 수 있다.Here, the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.
올레핀계 단량체는 C2-20 알파-올레핀(α-olefin), C1-20 디올레핀(diolefin), C3-20 사이클로올레핀(cycloolefin) 및 C3-20 사이클로디올레핀(cyclodiolefin)으로 구성되는 군으로부터 선택되는 적어도 하나이다.The olefinic monomer is composed of C 2-20 alpha-olefin (α-olefin), C 1-20 diolefin, C 3-20 cycloolefin and C 3-20 cyclodiolefin. at least one selected from the group.
예를 들어, 올레핀계 단량체는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센 또는 1-헥사데센 등일 수 있고, 올레핀계 중합체는 위에서 예시된 올레핀계 단량체를 1종만 포함하는 단독 중합체이거나 2종 이상 포함하는 공중합체일 수 있다.For example, the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 - may be dodecene, 1-tetradecene, 1-hexadecene, etc., and the olefinic polymer may be a homopolymer including only one type of the olefinic monomer exemplified above, or a copolymer including two or more types.
예시적인 실시예에서, 올레핀계 중합체는 에틸렌과 C3-20 알파-올레핀이 공중합된 공중합체일 수 있으며, 에틸렌과 1-헥센이 공중합된 공중합체가 바람직하나, 이들로 제한되는 것은 아니다.In an exemplary embodiment, the olefin-based polymer may be a copolymer of ethylene and C 3-20 alpha-olefin, preferably a copolymer of ethylene and 1-hexene, but is not limited thereto.
이 경우, 에틸렌의 함량은 55~99.9 중량%인 것이 바람직하고, 90~99.9 중량%인 것이 더욱 바람직하다. 알파-올레핀계 공단량체의 함량은 0.1~45 중량%가 바람 직하고, 0.1~10 중량%인 것이 더욱 바람직하다.In this case, it is preferable that the content of ethylene is 55 to 99.9 weight%, and it is more preferable that it is 90 to 99.9 weight%. The content of the alpha-olefin-based comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.
본 발명의 구체예에 따른 올레핀계 중합체는, 예를 들어 자유 라디칼(free radical), 양이온(cationic), 배위(coordination), 축합(condensation), 첨가(addition) 등의 중합반응에 의해 중합될 수 있으나, 이들로 제한되는 것은 아니다.The olefin-based polymer according to an embodiment of the present invention may be polymerized by, for example, a polymerization reaction such as free radical, cationic, coordination, condensation, and addition. However, it is not limited thereto.
바람직한 실시예로서, 올레핀계 중합체는 기상 중합법, 용액 중합법 또는 슬러리 중합법 등으로 제조될 수 있다. 올레핀계 중합체가 용액 중합법 또는 슬러리 중합법으로 제조되는 경우, 사용될 수 있는 용매의 예로서, 펜탄, 헥산, 헵탄, 노난, 데칸 및 이들의 이성질체와 같은 C5-12 지방족 탄화수소 용매; 톨루엔, 벤젠과 같은 방향족 탄화수소 용매; 디클로로메탄, 클로로벤젠과 같은 염소 원자로 치환된 탄화수소 용매; 및 이들의 혼합물 등을 들 수 있으나, 이들로 제한되는 것은 아니다.In a preferred embodiment, the olefin-based polymer may be prepared by a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. When the olefin-based polymer is prepared by a solution polymerization method or a slurry polymerization method, examples of the solvent that can be used include a C 5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof; aromatic hydrocarbon solvents such as toluene and benzene; hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; and mixtures thereof, but is not limited thereto.
실시예Example
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 단, 아래의 실시예는 본 발명을 예시하기 위한 것일 뿐이며, 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
실시예Example 1 One
위 화학식 3-1의 리튬 펜타메틸사이클로펜타디에나이드(lithium pentamethylcyclopentadienide) 72 ㎎(0.52 mmole, 1.2 eq.)을 상온에서 톨루엔 10 ㎖에 녹였다. 이를 천천히 교반하면서 -30℃에서 지르코늄 클로라이드(ZrCl4) 100 ㎎(0.43 mmole, 1.0 eq.)을 서서히 첨가한 후, 65℃에서 24시간 동안 교반하였다. -30℃까지 온도를 내린 후, 반응 혼합물에 위 화학식 4-1의 리튬 n-프로필사이클로펜타디에나이드(lithium n-propylcyclopentadienide) 147 ㎎(1.29 mmole, 3.0 eq.)와 하프늄 클로라이드(HfCl4) 137 ㎎(0.43 mmole, 1.0 eq.)을 서서히 첨가하였다. 이를 상온에서 22시간 교반하여 반응시켰다. 셀라이트 필터로 리튬 클로라이드(LiCl)를 제거한 후, 생성물을 건조시켜 위 화학식 1-1의 화합물((pentamethylcyclopentadienyl)(n-propylcyclopentadienyl) zirconium dichloride)과 위 화학식 2-1의 화합물(bis(n-propycyclopentadienyl) hafnium dichloride)의 혼합물 294 ㎎(수율: 77%)을 얻었다.72 mg (0.52 mmole, 1.2 eq.) of lithium pentamethylcyclopentadienide of Formula 3-1 above was dissolved in 10 ml of toluene at room temperature. With slow stirring, 100 mg (0.43 mmole, 1.0 eq.) of zirconium chloride (ZrCl 4 ) was slowly added at -30°C, followed by stirring at 65°C for 24 hours. Lower the temperature to -30 ℃, lithium n of Formula 4-1 above, the reaction mixture -propyl cyclopenta Deanna Id (lithium n -propylcyclopentadienide) 147 ㎎ ( . 1.29 mmole, 3.0 eq) and hafnium chloride (HfCl 4) 137 mg (0.43 mmole, 1.0 eq.) was added slowly. This was reacted by stirring at room temperature for 22 hours. After removing lithium chloride (LiCl) with a Celite filter, the product was dried and the compound of Formula 1-1 ((pentamethylcyclopentadienyl)( n- propylcyclopentadienyl) zirconium dichloride) and the compound of Formula 2-1 (bis( n- propycyclopentadienyl) ) hafnium dichloride) to obtain a mixture of 294 mg (yield: 77%).
1H NMR로 위 화학식 1-1과 위 화학식 2-1의 화합물의 혼성(3:2) 전이금속 화합물 구조를 확인하였다.A hybrid (3:2) transition metal compound structure of the compounds of Formula 1-1 and Formula 2-1 was confirmed by 1 H NMR.
1H-NMR (CDCl3, 300 MHz) 6.18 (t, 4H), 6.09-6.08 (m, 4H), 6.02 (t, 3H), 5.95-5.93 (m, 3H), 5.89-5.87 (m, 2H), 2.65-2.55 (m, 7H), 2.02 (s, 23H), 1.60-1.52 (m, 7H), 0.95-0.90 (m, 10.5H). 1 H-NMR (CDCl 3 , 300 MHz) 6.18 (t, 4H), 6.09-6.08 (m, 4H), 6.02 (t, 3H), 5.95-5.93 (m, 3H), 5.89-5.87 (m, 2H) ), 2.65-2.55 (m, 7H), 2.02 (s, 23H), 1.60-1.52 (m, 7H), 0.95-0.90 (m, 10.5H).
실시예Example 2 2
위 화학식 3-1의 리튬 펜타메틸사이클로펜타디에나이드 92 ㎎(0.65 mmole, 10.8 eq.)을 상온에서 톨루엔 10 ㎖에 녹였다. 이를 천천히 교반하면서 -30℃에서 지르코늄 클로라이드(ZrCl4) 125 ㎎(0.54 mmole, 9.0 eq.)을 서서히 첨가한 후, 65℃에서 12시간 동안 교반하였다. -30℃까지 온도를 내린 후, 반응 혼합물에 위 화학식 4-1의 리튬 n-프로필사이클로펜타디에나이드 82 ㎎(0.72 mmole, 12.1 eq.)와 하프늄 클로라이드(HfCl4) 19 ㎎(0.06 mmole, 1.0 eq.)을 서서히 첨가하였다. 이를 상온에서 7시간 교반하여 반응시켰다. 셀라이트 필터로 리튬 클로라이드(LiCl)를 제거한 후, 생성물을 건조시켜 위 화학식 1-1의 화합물과 위 화학식 2-1의 화합물의 혼합물 189 ㎎(수율: 77%)을 얻었다.92 mg (0.65 mmole, 10.8 eq.) of lithium pentamethylcyclopentadienide of Formula 3-1 above was dissolved in 10 ml of toluene at room temperature. 125 mg (0.54 mmole, 9.0 eq.) of zirconium chloride (ZrCl 4 ) was slowly added thereto at -30°C with slow stirring, followed by stirring at 65°C for 12 hours. After the temperature was lowered to -30°C, 82 mg (0.72 mmole, 12.1 eq.) of lithium n -propylcyclopentadienide of Formula 4-1 and hafnium chloride (HfCl 4 ) 19 mg (0.06 mmole, 1.0) were added to the reaction mixture. eq.) was added slowly. This was reacted by stirring at room temperature for 7 hours. After lithium chloride (LiCl) was removed with a Celite filter, the product was dried to obtain 189 mg (yield: 77%) of a mixture of the compound of Formula 1-1 and the compound of Formula 2-1.
1H NMR로 위 화학식 1-1과 위 화학식 2-1의 화합물의 혼성(100:7) 전이금속 화합물 구조를 확인하였다.A hybrid (100:7) transition metal compound structure of the compounds of Formula 1-1 and Formula 2-1 was confirmed by 1 H NMR.
1H-NMR (CDCl3, 600 MHz) 6.19 (t, 0.3H), 6.10 (t, 0.3H), 6.06 (t, 2H), 5.96 (t, 2H), 5.89-5.87 (t, 2H), 2.58 (t, 2H), 2.03 (s, 15H), 1.60-1.54 (m, 2H), 0.95-0.90 (m, 3H). 1 H-NMR (CDCl 3 , 600 MHz) 6.19 (t, 0.3H), 6.10 (t, 0.3H), 6.06 (t, 2H), 5.96 (t, 2H), 5.89-5.87 (t, 2H), 2.58 (t, 2H), 2.03 (s, 15H), 1.60-1.54 (m, 2H), 0.95-0.90 (m, 3H).
실시예Example 3 3
실시예 1에서 얻은 혼성 전이금속 화합물 288 ㎎(0.67 mmole, 1.0 eq.)을 상온에서 톨루엔 10 ㎖에 녹였다. 이를 천천히 교반하면서 -30℃까지 냉각시켰다. MeMgBr(500 ㎕, 2.2 eq.) 용액(디에틸 에테르 중의 3.0 M)을 천천히 주입한 후, 상온에서 3시간 교반하여 반응시켰다. 용매를 제거하고, 디클로로메탄 30 ㎖에 용해시킨 후 셀라이트 필터로 리튬 클로라이드를 제거하였다. 생성물을 건조시켜 화학식 1-13의 화합물과 화학식 1-13의 화합물의 혼합물 224 ㎎(수율: 88%)을 얻었다.288 mg (0.67 mmole, 1.0 eq.) of the hybrid transition metal compound obtained in Example 1 was dissolved in 10 ml of toluene at room temperature. It was cooled to -30°C with slow stirring. MeMgBr (500 μl, 2.2 eq.) solution (3.0 M in diethyl ether) was slowly injected, followed by stirring at room temperature for 3 hours to react. After removing the solvent and dissolving in 30 ml of dichloromethane, lithium chloride was removed through a Celite filter. The product was dried to obtain 224 mg (yield: 88%) of a mixture of the compound of Formula 1-13 and the compound of Formula 1-13.
1H NMR로 위 화학식 1-13의 화합물과 위 화학식 2-13의 화합물의 혼성(0.5:0.5) 전이금속 화합물 구조를 확인하였다.A hybrid (0.5:0.5) transition metal compound structure of the compound of Formula 1-13 and the compound of Formula 2-13 was confirmed by 1 H NMR.
1H-NMR (CDCl3, 300 MHz) 5.80 (t, 4H), 5.76 (t, 2H), 5.73 (t, 4H), 5.46 (t, 2H), 2.41 (t, 6H), 1.87 (s, 15H), 1.65-1.55 (m, 6H), 1.01-0.93 (m, 9H), -0.67 (s, 6H), -0.74 (s, 6H). 1 H-NMR (CDCl 3 , 300 MHz) 5.80 (t, 4H), 5.76 (t, 2H), 5.73 (t, 4H), 5.46 (t, 2H), 2.41 (t, 6H), 1.87 (s, 15H), 1.65-1.55 (m, 6H), 1.01-0.93 (m, 9H), -0.67 (s, 6H), -0.74 (s, 6H).
위 실시예의 반응물과 생성물의 조성비를 아래 표 1과 표 2에 나타내었다.The composition ratios of the reactants and products of the above examples are shown in Tables 1 and 2 below.
3-1chemical formula
3-1
5-1chemical formula
5-1
4-1chemical formula
4-1
6-1chemical formula
6-1
1-1chemical formula
1-1
2-1chemical formula
2-1
1-1chemical formula
1-1
2-1chemical formula
2-1
7-1chemical formula
7-1
1-13chemical formula
1-13
2-13chemical formula
2-13
본 발명의 구체예에 따른 이종의 전이금속 화합물을 포함하는 혼성 촉매 조성물 및 이를 포함하는 올레핀 중합용 촉매는 해당 전이금속 화합물의 함량에 따라서 우수한 가공성 및 기계적 물성을 갖는 다양한 폴리올레핀을 제조할 수 있다.The hybrid catalyst composition comprising a heterogeneous transition metal compound and the catalyst for olefin polymerization comprising the same according to an embodiment of the present invention can prepare various polyolefins having excellent processability and mechanical properties depending on the content of the corresponding transition metal compound.
또한, 혼성 촉매 조성물 및 이를 포함하는 올레핀 중합용 촉매를 제조하는 방법은 혼성 전이금속 화합물의 비율을 정밀하게 조절함으로써, 우수한 가공성 및 기계적 물성을 갖는 폴리올레핀 중합용 촉매를 용이하게 제공할 수 있다.In addition, the hybrid catalyst composition and the method for preparing a catalyst for olefin polymerization including the same can easily provide a catalyst for polyolefin polymerization having excellent processability and mechanical properties by precisely controlling the ratio of the hybrid transition metal compound.
Claims (30)
[화학식 1]
[화학식 2]
위 화학식 1과 화학식 2에서, M1과 M2는 서로 다르면서 각각 독립적으로 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이고,
X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도, C6-20 아릴아미도 또는 C1-20 알킬리덴이며,
R1 내지 R5와 R6 내지 R10은 각각 독립적으로 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이고, R1 내지 R5와 R6 내지 R10은 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있다.A hybrid catalyst composition comprising a transition metal compound represented by Formula 1 and Formula 2 below:
[Formula 1]
[Formula 2]
In Formulas 1 and 2, M 1 and M 2 are different and each independently titanium (Ti), zirconium (Zr) or hafnium (Hf),
each X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene;
R 1 to R 5 and R 6 to R 10 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1 -20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl; R 1 to R 5 and R 6 to R 10 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.
[화학식 1-1] [화학식 1-2] [화학식 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12]
[화학식 2-1] [화학식 2-2] [화학식 2-3]
[화학식 2-4] [화학식 2-5] [화학식 2-6]
[화학식 2-7] [화학식 2-8] [화학식 2-9]
[화학식 2-10] [화학식 2-11] [화학식 2-12]
.The method according to claim 3, wherein the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-12 below, and the transition metal compound represented by Formula 2 is selected from Formula 2- At least one of the transition metal compounds represented by 1 to 2-12, a hybrid catalyst composition:
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
[Formula 1-7] [Formula 1-8] [Formula 1-9]
[Formula 1-10] [Formula 1-11] [Formula 1-12]
[Formula 2-1] [Formula 2-2] [Formula 2-3]
[Formula 2-4] [Formula 2-5] [Formula 2-6]
[Formula 2-7] [Formula 2-8] [Formula 2-9]
[Formula 2-10] [Formula 2-11] [Formula 2-12]
.
[화학식 1-13] [화학식 1-14] [화학식 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21]
[화학식 1-22] [화학식 1-23] [화학식 1-24]
[화학식 2-13] [화학식 2-14] [화학식 2-15]
[화학식 2-16] [화학식 2-17] [화학식 2-18]
[화학식 2-19] [화학식 2-20] [화학식 2-21]
[화학식 2-22] [화학식 2-23] [화학식 2-24]
.The method according to claim 4, wherein the transition metal compound represented by Formula 1 is at least one of the transition metal compounds represented by Formulas 1-13 to 1-24 below, and the transition metal compound represented by Formula 2 is represented by Formula 2- 13 to at least one of the transition metal compounds represented by 2-24, a hybrid catalyst composition:
[Formula 1-13] [Formula 1-14] [Formula 1-15]
[Formula 1-16] [Formula 1-17] [Formula 1-18]
[Formula 1-19] [Formula 1-20] [Formula 1-21]
[Formula 1-22] [Formula 1-23] [Formula 1-24]
[Formula 2-13] [Formula 2-14] [Formula 2-15]
[Formula 2-16] [Formula 2-17] [Formula 2-18]
[Formula 2-19] [Formula 2-20] [Formula 2-21]
[Formula 2-22] [Formula 2-23] [Formula 2-24]
.
[화학식 3]
[화학식 4]
[화학식 5]
M1X4
[화학식 6]
M2X4
위 화학식 1 내지 6에서, X가 할로겐이고, M1, M2, R1 내지 R5와 R6 내지 R10은 제1항에서 정의된 바와 같다.(1) dissolving the compound represented by Formula 3 below in a solvent; (2) adding a compound represented by the following formula (5) to the solution obtained in step (1), followed by reacting with stirring; (3) The compound represented by Formula 4 and the compound represented by Formula 6 below are added to the reaction mixture obtained in step (2) and reacted under stirring, including the transition metal compound represented by Formula 1 and Formula 2 An equivalent ratio of the compound represented by Formula 3 added in step (1) to the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1, including obtaining a first hybrid catalyst composition to and the equivalent ratio of the compound represented by Formula 5 added in step (2) to the compound represented by Formula 6 added in step (3) is 1:100 to 100:1, the method for preparing a hybrid catalyst composition:
[Formula 3]
[Formula 4]
[Formula 5]
M 1 X 4
[Formula 6]
M 2 X 4
In Formulas 1 to 6, X is halogen, M 1 , M 2 , R 1 to R 5 and R 6 to R 10 are as defined in claim 1.
[화학식 3-1] [화학식 3-2] [화학식 3-3]
[화학식 3-4] [화학식 3-5] [화학식 3-6]
.The method for preparing a hybrid catalyst composition according to claim 7, wherein in the step (1), the compound represented by Formula 3 is at least one of the compounds represented by Formulas 3-1 to 3-6 below:
[Formula 3-1] [Formula 3-2] [Formula 3-3]
[Formula 3-4] [Formula 3-5] [Formula 3-6]
.
[화학식 4-1] [화학식 4-2] [화학식 4-3]
[화학식 4-4] [화학식 4-5] [화학식 4-6]
[화학식 4-7] [화학식 4-8] [화학식 4-9]
[화학식 4-10] [화학식 4-11] [화학식 4-12]
.The method for preparing a hybrid catalyst composition according to claim 7, wherein in the step (3), the compound represented by Formula 4 is at least one of the compounds represented by Formulas 4-1 to 4-12 below:
[Formula 4-1] [Formula 4-2] [Formula 4-3]
[Formula 4-4] [Formula 4-5] [Formula 4-6]
[Formula 4-7] [Formula 4-8] [Formula 4-9]
[Formula 4-10] [Formula 4-11] [Formula 4-12]
.
[화학식 7a]
XaMgXb
[화학식 7b]
XcLi
위 화학식 7a와 7b에서, Xa와 Xc는 각각 독립적으로 C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도, C6-20 아릴아미도 또는 C1-20 알킬리덴이고, Xb는 할로겐이다.8. The method of claim 7, further comprising the steps of: (3a) dissolving the first hybrid catalyst composition in a solvent; And (3b) to the solution obtained in step (3a), the compound represented by the following formula 7a, the compound represented by the formula 7b, or ammonium hydrogen fluoride (NH 4 HF 2 ) is added and reacted under stirring, and the above formula 1 and Method for preparing a hybrid catalyst composition, further comprising the step of obtaining a second hybrid catalyst composition comprising a transition metal compound represented by Formula 2:
[Formula 7a]
X a MgX b
[Formula 7b]
X c Li
In the above formulas 7a and 7b, X a and X c are each independently C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6- 20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene, and X b is halogen.
[화학식 8]
[화학식 9]
[화학식 10]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]-
위 화학식 8에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소기 또는 할로겐으로 치환된 C1-20 탄화수소기이고,
위 화학식 9에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이며,
위 화학식 10에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다.The catalyst for olefin polymerization according to claim 21, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by Formula 8, a compound represented by Formula 9, and a compound represented by Formula 10:
[Formula 8]
[Formula 9]
[Formula 10]
[LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
In the above formula (8), n is an integer of 2 or more, R a is a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen,
In Chemical Formula 9, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a halogen-substituted C 1-20 hydrocarbon group. Or a C 1-20 alkoxy group,
In the above formula (10), L is a neutral or cationic Lewis base, [LH] + and [L] + are a Bronsted acid, Z is a group 13 element, A is each independently substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group.
[화학식 1]
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 5]
M1X4
[화학식 6]
M2X4
위 화학식 1 내지 6에서, X가 할로겐이고, M1, M2, R1 내지 R5와 R6 내지 R10은 제1항에서 정의된 바와 같다.(1) dissolving the compound represented by Formula 3 below in a solvent; (2) adding a compound represented by the following formula (5) to the solution obtained in step (1), followed by reacting with stirring; (3) The compound represented by Formula 4 and the compound represented by Formula 6 below are added to the reaction mixture obtained in step (2) and reacted under stirring, including the transition metal compound represented by Formula 1 and Formula 2 obtaining a first hybrid catalyst composition to and (4) supporting the hybrid catalyst composition, the cocatalyst compound, or both on a carrier, wherein the compound represented by Formula 3 added in step (1) vs. the compound represented by Formula 5 added in step (2) is 1:1 to 1.5:1, and the equivalent ratio of the compound represented by Formula 5 added in step (2) to the compound represented by Formula 6 added in step (3) is 1:100 to 100:1 , A method for preparing a catalyst for olefin polymerization:
[Formula 1]
[Formula 2]
[Formula 3]
[Formula 4]
[Formula 5]
M 1 X 4
[Formula 6]
M 2 X 4
In Formulas 1 to 6, X is halogen, M 1 , M 2 , R 1 to R 5 and R 6 to R 10 are as defined in claim 1.
[화학식 7a]
XaMgXb
[화학식 7b]
XcLi
위 화학식 7a와 7b에서, Xa, Xb 및 Xc는 제15항에서 정의된 바와 같다.30. The method of claim 29, further comprising the steps of: (3a) dissolving the first hybrid catalyst composition in a solvent; And (3b) to the solution obtained in step (3a), the compound represented by the following formula 7a, the compound represented by the formula 7b, or ammonium hydrogen fluoride (NH 4 HF 2 ) is added and reacted under stirring, and the above formula 1 and A method for preparing a catalyst for olefin polymerization, further comprising the step of obtaining a second hybrid catalyst composition comprising a transition metal compound represented by Formula 2:
[Formula 7a]
X a MgX b
[Formula 7b]
X c Li
In Formulas 7a and 7b, X a , X b and X c are as defined in claim 15 .
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KR102668044B1 (en) | 2024-05-23 |
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US20230192911A1 (en) | 2023-06-22 |
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